TWI744286B - Radiation-sensitive composition, optical filter, laminate, pattern forming method, solid-state imaging element, image display device, and infrared sensor - Google Patents

Abstract

The present invention provides a radiation-sensitive composition that can form a pattern with good infrared shielding properties and excellent rectangularity. The radiation-sensitive composition includes a near-infrared absorber, a resin, a radical polymerizable compound, and a photo-radical polymerization initiator, and has a maximum absorption wavelength in the range of 700 nm to 1000 nm, and the absorbance at the maximum absorption wavelength Amax , The ratio of the absorbance A550 to the absorbance A550 at a wavelength of 550nm, that is, the absorbance Amax/absorbance A550 is 50~500, the resin contains a resin having an acid group, and the mass ratio of a radical polymerizable compound to a resin having an acid group is a radical polymerizable compound/ Resin with acid group=0.3~0.7.

Description

Radiation-sensitive composition, optical filter, laminate, image Case forming method, solid-state imaging element, image display device and infrared sensor

The invention relates to a radiation-sensitive composition, an optical filter, a laminate, a pattern forming method, a solid-state imaging element, an image display device, and an infrared sensor.

In video cameras, digital still cameras, mobile phones with camera functions, etc., Charge Coupled Devices (CCD) or complementary metal oxides have been used as solid-state imaging elements for color images. Film semiconductor (Complementary Metal Oxide Semiconductor, CMOS). These solid-state imaging devices use silicon photodiodes that are sensitive to infrared in their light receiving parts, so they sometimes use a near-infrared cut filter for visual sensitivity correction.

Regarding the near-infrared cut filter, a method of manufacturing it using a radiation-sensitive composition containing a near-infrared absorber in order to improve infrared shielding properties is known. For example, Patent Document 1 describes the use of a radiation-sensitive composition containing a pyrrolopyrrole compound to produce a near-infrared cut filter and the like. Patent Document 2 describes the use of a radiation-sensitive composition containing cesium tungsten oxide to produce a near-infrared cut filter and the like. Patent Document 3 describes the use of a radiation-sensitive composition containing naphthalocyanine and the like to produce a near-infrared cut filter and the like.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-191190

[Patent Document 2] Japanese Patent Laid-Open No. 2013-137337

[Patent Document 3] Japanese Patent Laid-Open No. 2014-224921

Previously, a near-infrared cut filter was used as a flattening film. In recent years, near-infrared cut filters have also been studied for pattern formation and use. For example, it is being studied to use each pixel (for example, red pixel, blue pixel, green pixel, etc.) forming a color filter on the pattern of the near-infrared cut filter. When manufacturing such a laminate, it is desirable that the pattern of the near-infrared cut filter has good rectangularity. If the pattern of the near-infrared cut filter has good rectangularity, when the pixels of the color filter are formed on the pattern of the near-infrared cut filter to form a laminate, the generation of voids, color mixing, and the like can be suppressed.

However, according to research conducted by the inventors, it has been found that, compared with the case of forming a pixel pattern such as a color filter using a coloring composition containing a color colorant, it is better than a radiation-sensitive composition containing a near-infrared absorber. In the case of forming a pattern with an object, the rectangularity tends to be deteriorated. In addition, the previously widely known radiation-sensitive composition containing a near-infrared absorber is not a composition that is used assuming that it is patterned. In addition, the conventionally known radiation-sensitive composition cannot be said to have sufficient rectangularity, and further improvement of the rectangularity is desired.

Therefore, an object of the present invention is to provide a radiation-sensitive composition that can form a pattern with good infrared shielding properties and excellent rectangularity. In addition, an object of the present invention is to provide an optical filter, a laminate, a pattern forming method, a solid-state imaging device, an image display device, and an infrared sensor.

Based on the circumstances, the inventors of the present invention conducted diligent studies, and as a result, found that the above-mentioned object can be achieved by using the radiation-sensitive composition described later, and the present invention has been completed. The present invention provides the following.

<1> A radiation-sensitive composition comprising a near-infrared absorber, a resin, a radical polymerizable compound, and a photo-radical polymerization initiator, and the radiation-sensitive composition has a maximum absorption wavelength in the range of 700nm~1000nm , The ratio of the absorbance Amax at the maximum absorption wavelength to the absorbance A550 at the wavelength of 550nm, that is, the absorbance Amax/absorbance A550 is 50 to 500. The resin contains resins with acid groups, and the mass of radical polymerizable compounds and resins with acid groups The ratio is a radical polymerizable compound/resin having an acid group=0.3 to 0.7.

<2> The radiation-sensitive composition according to <1>, wherein the resin includes an alkali-soluble resin, and the mass ratio of the radical polymerizable compound to the alkali-soluble resin is radical polymerizable compound/alkali-soluble resin=0.3~0.7 .

<3> The radiation-sensitive composition according to <1> or <2>, wherein the photoradical polymerization initiator contains an oxime compound.

<4> The radiation-sensitive composition according to <1> or <2>, wherein the photoradical polymerization initiator includes an oxime compound and an α-aminoketone compound.

<5> The radiation-sensitive composition according to any one of <1> to <4>, wherein the radical polymerizable compound is a radical polymerizable compound containing an acid group.

<6> The radiation-sensitive composition according to any one of <1> to <5>, which further contains a chain transfer agent.

<7> The radiation-sensitive composition according to any one of <1> to <6>, which further contains an ultraviolet absorber.

<8> The radiation-sensitive composition according to any one of <1> to <7>, wherein the near-infrared absorber contains at least one selected from organic pigments and inorganic pigments.

<9> The radiation-sensitive composition according to any one of <1> to <7>, wherein the total solid content of the radiation-sensitive composition contains 20% by mass or more of a near-infrared absorber.

<10> An optical filter using the radiation-sensitive composition according to any one of <1> to <9>.

<11> The optical filter according to <10>, wherein the optical filter is a near infrared cut filter or an infrared transmission filter.

<12> The optical filter according to <10> or <11>, which further has an anti-reflection film.

<13> A laminate having a near-infrared cut filter using the radiation-sensitive composition as described in any one of <1> to <9>, and a layer containing color Color filter of the agent.

<14> A pattern forming method, comprising: using the radiation-sensitive composition as described in any one of <1> to <9> to form a radiation-sensitive composition layer on a support; The step of exposing the radiation-sensitive composition layer; and the step of developing and removing the unexposed part to form a pattern.

<15> The pattern forming method as described in <14>, which further includes a step of exposing after developing and removing the unexposed part.

<16> A solid-state imaging element having the optical filter according to any one of <10> to <12>.

<17> An image display device having the optical filter according to any one of <10> to <12>.

<18> An infrared sensor having the optical filter according to any one of <10> to <12>.

According to the present invention, it is possible to provide a radiation-sensitive composition that can form a pattern with good infrared shielding properties and excellent rectangularity. In addition, the present invention can provide an optical filter, a laminate, a pattern forming method, a solid-state imaging device, an image display device, and an infrared sensor.

110: solid-state image sensor

111: Near infrared cut filter

112: Color filter

114: Infrared transmission filter

115: Micro lens

116: Planarization layer

hν: incident light

Fig. 1 is a schematic diagram showing an embodiment of an infrared sensor.

Hereinafter, the content of the present invention will be described in detail.

In this specification, the term "~" is used to include the numerical values described before and after it as the lower limit and the upper limit.

In the expression of the group (atomic group) in this specification, the expression that does not describe substituted and unsubstituted includes a group (atomic group) that does not have a substituent, and also includes a group (atomic group) having a substituent. For example, the "alkyl group" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group).

In this specification, the term "exposure", unless otherwise specified, includes not only exposure using light, but also drawing using particle beams such as electron beams and ion beams. In addition, as the light used in the exposure, generally, the bright-line spectrum of a mercury lamp, extreme ultraviolet light represented by excimer lasers, extreme ultraviolet light (Extreme Ultraviolet (EUV) light), X-rays, electron beams, etc. Actinic rays or radiation.

In this specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic and methacrylic acid, and "(meth)acryloyl" means acryloyl and methacrylic acid. Base acrylic acid base.

In this specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene conversion values measured by Gel Permeation Chromatography (GPC).

The so-called near-infrared rays refer to light (electromagnetic waves) with a wavelength of 700nm to 2500nm in the maximum absorption wavelength region.

In this specification, the term "step" not only refers to an independent step, but even when it cannot be clearly distinguished from other steps, as long as the desired effect of the step is achieved, it is included in this term.

<Radiation Sensing Composition>

The radiation-sensitive composition of the present invention (hereinafter also referred to as the composition) is a radiation-sensitive composition containing a near-infrared absorber, a resin, a radical polymerizable compound, and a photo-radical polymerization initiator. The composition has a maximum absorption wavelength in the range of 700nm~1000nm. The ratio of the absorbance Amax at the maximum absorption wavelength to the absorbance A550 at a wavelength of 550nm, that is, the absorbance Amax/absorbance A550 is 50 to 500. The resin contains a resin with an acid group. The mass ratio of the radical polymerizable compound to the resin having an acid group is radical polymerizable compound/resin having an acid group=0.3 to 0.7.

By using the radiation-sensitive composition described above, a pattern having excellent infrared shielding properties and excellent rectangularity can be formed. The radiation-sensitive composition of the present invention contains a near-infrared absorber, and the absorbance Amax/absorbance A550 is 50 to 500, so it can form a pattern with excellent infrared shielding properties. Furthermore, by including a radical polymerizable compound and a resin having an acid group in a ratio of radical polymerizable compound/resin having an acid group=0.3 to 0.7 in terms of mass ratio, a pattern with excellent rectangularity can be formed. That is, when the radiation-sensitive composition of the present invention is used to form a pattern, when the mask is interposed and exposed, the curability of the radiation-sensitive composition at the periphery of the mask can be improved. Moreover, by combining radically polymerizable compounds/resins with acid groups When it is set to 0.3 or more, the lower side of the pattern (the support side of the film) is less likely to become smaller than the design value, and the generation of undercuts (overhanging shapes) can be suppressed. In addition, by setting the radical polymerizable compound/resin having an acid group to 0.7 or less, the upper side of the pattern (the surface side of the film) is less likely to become smaller than the design value, thereby suppressing overcutting (positive cone shape) produce. Therefore, a pattern with excellent rectangularity can be formed. Furthermore, by including a radical polymerizable compound and a resin having an acid group in a ratio of radical polymerizable compound/resin having an acid group=0.3 to 0.7 in terms of mass ratio, the generation of residues during pattern formation can also be suppressed.

The radiation-sensitive composition has a maximum absorption wavelength in the range of 700 nm to 1000 nm, more preferably has a maximum absorption wavelength in the range of 720 nm to 980 nm, and more preferably has a maximum absorption wavelength in the range of 740 nm to 960 nm. In addition, the absorbance Amax/absorbance A550 of the radiation-sensitive composition of the present invention is 50 to 500, preferably 70 to 450, and more preferably 100 to 400. The absorbance condition can be achieved by any means. By adjusting the type and content of the near-infrared absorber, the absorbance condition can be better achieved.

The absorbance Aλ at a certain wavelength λ can be defined by the following formula.

Aλ=-log(Tλ)

Aλ is the absorbance at the wavelength λ, and Tλ is the transmittance at the wavelength λ.

In the present invention, the value of absorbance is preferably a value in a film produced using a radiation-sensitive composition. The absorbance can be measured using a previously known spectrophotometer.

One of the preferable aspects of the radiation-sensitive composition of the present invention is to further include a chain transfer agent. According to this aspect, the hardening of the film surface at the time of exposure of the radiation-sensitive composition can be promoted. Therefore, it is possible to suppress the reduction of the film thickness during exposure, etc., and it is easy to form a pattern with more excellent rectangularity.

In addition, one of the preferable aspects of the radiation-sensitive composition of the present invention further contains an ultraviolet absorber. According to this aspect, when the radiation-sensitive composition of the present invention is exposed to the barrier mask, the curability of the radiation-sensitive composition at the periphery of the mask can be improved. Therefore, it is easy to form a pattern with more excellent rectangularity.

In addition, one of the preferred aspects of the radiation-sensitive composition of the present invention is to include an oxime compound and an α-aminoketone compound as a photo-radical polymerization initiator. According to this aspect, the combined use of energy-moving radical generation prevents the upper side of the pattern (the surface side of the film) from becoming thinner than the design value, suppresses the occurrence of overcutting, and improves the rectangularity.

Hereinafter, each component of the radiation-sensitive composition of the present invention will be described.

<<Near Infrared Absorbent>>

The radiation-sensitive composition of the present invention (hereinafter, also referred to as the composition of the present invention) contains a near-infrared absorber. Furthermore, in the present invention, the near-infrared absorber refers to a material that has absorption in the near-infrared region (preferably in the range of 700 nm to 1300 nm in wavelength, and more preferably in the range of 700 nm to 1000 nm in wavelength).

The near-infrared absorber preferably contains one having a maximum absorption wavelength in the range of 700 nm to 1000 nm, the absorbance Amax at the maximum absorption wavelength, and the absorbance A550 at a wavelength of 550 nm, that is, the absorbance Amax/absorbance A550 of 50 to 500 Near-infrared absorbing compound (hereinafter, also referred to as near-infrared absorbing compound A). In addition, when a composition containing 26% by mass of the near-infrared absorbing compound A in the total solid content is used to form a film with a thickness of 0.7 μm, the near-infrared absorbing compound A is preferably absorbance Amax/absorbance A550 in the film A compound that satisfies the spectral characteristics of 50 to 500. The upper limit is more preferably 450 or less, and still more preferably 400 or less. The lower limit is more preferably 70 or more, and still more preferably 100 or more. According to this aspect, it is easy to produce a pattern excellent in visible transparency and infrared shielding properties.

The near-infrared absorbing compound A may be any of pigments and dyes. Since it is easy to form a pattern excellent in rectangularity, a pigment is preferable. In addition, the pigment may be an organic pigment or an inorganic pigment. From the viewpoint of spectral characteristics, organic pigments are preferred.

Furthermore, in the present invention, the term "pigment" refers to a compound that is difficult to dissolve in a specific solvent. For example, with respect to any solvent of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, cyclopentanone, and diethylene glycol monobutyl ether acetate at 23°C, the solubility of the pigment is preferably 0.1 % By mass or less, more preferably 0.01% by mass or less.

If the near-infrared absorbing compound A is a compound having a maximum absorption wavelength in the range of 700 nm to 1000 nm, and the absorbance Amax/absorbance A550 is 50 to 500, it is not particularly limited. Examples include: pyrrolopyrrole compounds, cyanine compounds, squaraine compounds, phthalocyanine compounds, naphthalocyanine compounds, perylene compounds, merocyanine compounds, croconium compounds, oxonine compounds, diiminium Compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, etc. That Among them, pyrrolopyrrole compounds, cyanine compounds, squaraine compounds, phthalocyanine compounds, naphthalocyanine compounds, and perylene compounds are preferred, and pyrrolopyrrole compounds, cyanine compounds, and squaraine compounds are more preferred. The compound is more preferably a pyrrolopyrrole compound.

In addition, IRA828, IRA842, IRA848, IRA850, IRA851, IRA866, IRA870, IRA884 (manufactured by Exiton), SDO-C33 (manufactured by Yumoto Chemical Industry Co., Ltd.) can also be used for near-infrared absorbing compound A, Escala (EX color) IR-14, Escala (EX color) IR-10A, Escala (EX color) TX-EX-801B, Escala (EX color) TX-EX-805K, ES Kara (EX color) TX-EX-815K (manufactured by Nippon Shokubai Co., Ltd.), Shigenox NIA-8041, Shigenox NIA-8042, Shigenox NIA -814, Shigenox NIA-820, Shigenox NIA-839 (manufactured by Hakkol Chemical (stock)), Epolite V-63, Epolight 3801, Epolight 3036 (manufactured by EPOLIN), PRO-JET825LDI (manufactured by Fujifilm (stock)), NK-3027, NKX-113, NKX -1199, SMP-363, SMP-387, SMP-388, SMP-389 (manufactured by Hayashibara Co., Ltd.), YKR-3070 (manufactured by Mitsui Chemicals Co., Ltd.), etc.

The content of the near-infrared absorbing compound A of the near-infrared absorbing agent is preferably 60% by mass or more. The upper limit may be 100% by mass, 90% by mass or less, or 80% by mass or less. The lower limit is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more.

The content of the pigment of the near-infrared absorber is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. The upper limit can also be set to 100% by mass.

The content of the near-infrared absorber in the composition of the present invention is preferably 20% by mass or more with respect to the total solid content of the composition of the present invention. The upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less. By setting it within this range, a pattern having excellent infrared shielding properties and excellent rectangularity can be formed. In addition, in the case where the near-infrared absorbing agent contains only the near-infrared absorbing compound A, the content of the near-infrared absorbing agent corresponds to the content of the near-infrared absorbing compound A. In addition, when the near-infrared absorbing agent contains the near-infrared absorbing compound A and another near-infrared absorbing compound described later, the total amount of the near-infrared absorbing compound A and the other near-infrared absorbing compound described later is the content of the near-infrared absorbing agent.

The content of the near-infrared absorbing compound A in the composition of the present invention is preferably 20% by mass or more with respect to the total solid content of the composition of the present invention. The upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less. By setting it within this range, a pattern having excellent infrared shielding properties and excellent rectangularity can be formed.

(Pyrrolopyrrole compound)

In the present invention, the pyrrolopyrrole compound is preferably a compound represented by the following formula (I). The following compounds are preferably compounds having the aforementioned absorbance ratio.

[化1]

In formula (I), A ¹ and A ² each independently represent a heteroaryl group, B ¹ and B ² each independently represent a -BR ¹ R ² group, R ¹ and R ² each independently represent a substituent, R ¹ and R ² may be bonded to each other to form a ring, C ¹ and C ² each independently represent an alkyl group, an aryl group, or a heteroaryl group, and D ¹ and D ² each independently represent a substituent.

In formula (I), A ¹ and A ² each independently represent a heteroaryl group. A ¹ and A ² may be the same group or different groups. A ¹ and A ^{2 are} preferably the same group.

The heteroaryl group is preferably a monocyclic ring or a condensed ring, and is preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 8, more preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 4. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the heteroaryl group is preferably 3-30, more preferably 3-18, still more preferably 3-12, and particularly preferably 3-10. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring.

The heteroaryl group is preferably a group represented by the following formula (A-1) and a group represented by the following formula (A-2).

[化2]

In formula (A-1), X ¹ each independently represents O, S, NR ^X1 or CR ^X2 R ^X3 , R ^X1 to R ^X3 each independently represent a hydrogen atom or a substituent, and R ³ and R ⁴ each independently represent A hydrogen atom or a substituent, R ³ and R ⁴ may be bonded to each other to form a ring. * Indicates the bonding position with formula (I).

The substituents represented by R ³ , R ⁴ and R ^X1 to R ^X3 include alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, acyl groups, and alkoxy groups. Carbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, acyloxy, amino, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, heteroaryloxycarbonylamino, sulfonamide Amino group, sulfamylsulfonyl, carbamethanyl, alkylthio, arylthio, heteroarylthio, alkylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylsulfinyl Amino, arylsulfinyl, heteroarylsulfinyl, ureido, phosphate amide, sulfhydryl, sulfo, carboxy, nitro, hydroxylamine, sulfinate, hydrazine, imine Groups, silyl groups, hydroxyl groups, halogen atoms, cyano groups, etc., preferably alkyl groups, aryl groups, and halogen atoms.

The carbon number of the alkyl group is preferably 1-20, more preferably 1-15, and still more preferably 1-8. The alkyl group may be any of linear, branched, and cyclic, and is preferably linear or branched. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the above-mentioned groups, for example, a halogen atom, an aryl group, and the like.

The carbon number of the aryl group is preferably 6-30, more preferably 6-20, and still more preferably 6-12. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include the above-mentioned groups, for example, a halogen atom, an alkyl group, and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The ring formed by bonding R ³ and R ^{4 is preferably an aromatic ring.} When R ³ and R ⁴ form a ring, the group represented by the formula (A-1) includes the group represented by the following (A-1-1) and the group represented by (A-1-2)的基等。 The base and so on.

In the formula, X ¹ each independently represents O, S, NR ^X1 or CR ^X2 R ^X3 , R ^X1 ~R ^X3 each independently represents a hydrogen atom or a substituent, and R ¹⁰¹ ~R ¹⁰⁹ each independently represents a hydrogen atom or a substituent . * Indicates the bonding position with formula (I).

In formula (A-2), Y ¹ to Y ⁴ independently represent N or CR ^Y1 , at least two of ^{Y 1} to Y ^{4 are CR Y1} , R ^Y1 represents a hydrogen atom or a substituent, and adjacent R ^Y1 may be mutually exclusive Bonded to each other to form a ring. * Indicates the bonding position with formula (I).

The substituent represented by R ^Y1 includes the above-mentioned substituents, and an alkyl group, an aryl group, and a halogen atom are preferable. The carbon number of the alkyl group is preferably 1-20, more preferably 1-15, and still more preferably 1-8. The alkyl group may be any of linear, branched, and cyclic, and is preferably linear or branched. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the above-mentioned substituents, for example, a halogen atom, an aryl group, and the like.

The carbon number of the aryl group is preferably 6-30, more preferably 6-20, and still more preferably 6-12. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include the above-mentioned substituents, for example, a halogen atom, an alkyl group, and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

At least two of Y ¹ to Y ^{4 are CR Y1} , and adjacent R ^Y1 may be bonded to each other to form a ring. The ring formed by bonding adjacent R ^{Y1 to} each other is preferably an aromatic ring. When adjacent R ^Y1 form a ring with each other, the group represented by the following (A-2-1) to (A-2-5) etc. can be mentioned as a group represented by formula (A-2).

In the formula, R ²⁰¹ to R ²²⁷ each independently represent a hydrogen atom or a substituent, and * represents a bonding position to the formula (I).

Specific examples of A ¹ and A ² include the following. In the following, Bu means butyl. * Indicates the bonding position with formula (I).

[化6]

In formula (I), B ¹ and B ² each independently represent a -BR ¹ R ² group, and R ¹ and R ² each independently represent a substituent. R ¹ and R ² may be bonded to each other to form a ring. Examples of the substituent include the groups described in A ¹ and A ² above, and are preferably a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or a heteroaryl group, and more preferably a halogen atom, an aryl group, or a heteroaryl group. The heteroaryl group is more preferably an aryl group or a heteroaryl group. R ¹ and R ² may be the same group or different groups. R ¹ and R ^{2 are} preferably the same group. In addition, B ¹ and B ² may be the same group or different groups. B ¹ and B ^{2 are} preferably the same group.

The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and particularly preferably a fluorine atom.

The carbon number of the alkyl group is preferably 1-40. The lower limit is more preferably 3 or more, for example. The upper limit is, for example, more preferably 30 or less, and still more preferably 25 or less. The alkyl group may be any of linear, branched, and cyclic, and is preferably linear or branched.

The carbon number of the alkenyl group is preferably 2-40. The lower limit is, for example, more preferably 3 or more, still more preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The alkenyl group may be any of linear, branched, and cyclic.

The carbon number of the alkoxy group is preferably 1-40. The lower limit is more preferably 3 or more, for example. Upper limit For example, it is more preferably 30 or less, and still more preferably 25 or less. The alkoxy group may be any of linear, branched, and cyclic.

The carbon number of the aryl group is preferably 6-20, more preferably 6-12. The aryl group may have a substituent or may be unsubstituted. As a substituent, an alkyl group, an alkoxy group, a halogen atom, etc. are mentioned. Regarding these details, the above-mentioned ones can be cited.

Heteroaryl groups may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the heteroaryl group is preferably 3-30, more preferably 3-18, still more preferably 3-12, and particularly preferably 3-5. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group may have a substituent or may be unsubstituted. As a substituent, an alkyl group, an alkoxy group, a halogen atom, etc. are mentioned. Regarding these details, the above-mentioned ones can be cited.

R ¹ and R ^{2 of the} -BR ¹ R ² group may be bonded to each other to form a ring. For example, the structures shown in the following (B-1) to (B-4), etc. are mentioned. In the following, R represents a substituent, ^Ra1 to ^Ra4 each independently represent a hydrogen atom or a substituent, m1 to m3 each independently represent an integer of 0 to 4, and * represents a bonding position with formula (I). As the substituent groups R and R ^a1 ~ R ^a4 represented substitution described in the ^second group include R ¹ and R, it is preferably an alkyl group and a halogen atom.

[化7]

As ^{specific examples of B 1} and B ² , the following can be cited. In the following, Me represents a methyl group, and Bu represents a butyl group. * Indicates the bonding position with formula (I).

In formula (I), C ¹ and C ² each independently represent an alkyl group, an aryl group, or a heteroaryl group. C ¹ and C ² may be the same group or different groups. C ¹ and C ^{2 are} preferably the same group. Preferably, C ¹ and C ² are each independently an aryl group or a heteroaryl group, and more preferably an aryl group.

The carbon number of the alkyl group is preferably 1-40, more preferably 1-30, and particularly preferably 1-25. The alkyl group may be any of linear, branched, and cyclic, preferably linear or branched, and particularly preferably branched.

The aryl group is preferably an aryl group having 6 to 20 carbons, and more preferably an aryl group having 6 to 12 carbons. Particularly preferred is phenyl or naphthyl.

Heteroaryl groups may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the heteroaryl group is preferably 3-30, more preferably 3-18, and still more preferably 3-12.

The alkyl group, aryl group, and heteroaryl group may have a substituent or may be unsubstituted. It preferably has a substituent.

Examples of the substituent include: a hydrocarbon group that may contain an oxygen atom, an amino group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a heteroaryloxycarbonylamino group, a sulfonylamino group, Aminosulfonyl, carbamethanyl, alkylthio, arylthio, heteroarylthio, alkylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylsulfinyl, aromatic Sulfinyl group, heteroaryl sulfinyl group, ureido group, phosphate amide group, sulfhydryl group, sulfo group, carboxyl group, nitro group, hydroxylamino acid group, sulfinic acid group, hydrazine group, imino group, silyl group , Hydroxyl, halogen atom, cyano group, etc.

Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine. Atom etc.

As a hydrocarbon group, an alkyl group, an alkenyl group, an aryl group, etc. are mentioned.

The carbon number of the alkyl group is preferably 1-40. The lower limit is more preferably 3 or more, still more preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The alkyl group may be any of linear, branched, and cyclic, preferably linear or branched, and particularly preferably branched. The carbon number of the branched alkyl group is preferably 3-40. The lower limit is, for example, more preferably 5 or more, still more preferably 8 or more, and still more preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The number of branches of the branched alkyl group is preferably 2-10, and more preferably 2-8, for example.

The carbon number of the alkenyl group is preferably 2-40. The lower limit is, for example, more preferably 3 or more, still more preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The alkenyl group may be any of linear, branched, and cyclic, preferably linear or branched, and particularly preferably branched. The carbon number of the branched alkenyl group is preferably 3-40. The lower limit is, for example, more preferably 5 or more, still more preferably 8 or more, and still more preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The number of branches of the branched alkenyl group is preferably 2-10, more preferably 2-8.

The carbon number of the aryl group is preferably 6-30, more preferably 6-20, and still more preferably 6-12.

As a hydrocarbon group containing an oxygen atom, the group represented by ^{-LR x1 is mentioned.}

L represents -O-, -CO-, -COO-, -OCO-, -(OR ^x2 ) _m -or -(R ^x2 O) _m -. R ^x1 represents an alkyl group, an alkenyl group or an aryl group. R ^x2 represents an alkylene group or an arylene group. m represents an integer of 2 or more, and m pieces of R ^x2 may be the same or different.

L is preferably -O-, -(OR ^x2 ) _m -or -(R ^x2 O) _m -, more preferably -O-.

The meanings of the alkyl group, alkenyl group, and aryl group represented by R ^x1 are the same as those described above, and the preferred ranges are also the same. R ^{x1 is} preferably an alkyl group or an alkenyl group, more preferably an alkyl group.

The ^{number of carbon atoms in the alkylene group represented by R x2} is preferably from 1 to 20, more preferably from 1 to 10, and still more preferably from 1 to 5. The alkylene group may be linear, branched, and cyclic, and is preferably linear or branched. The carbon number of the arylene group represented by R ^{x2 is preferably 6-20, more preferably 6-12.} R ^{x2 is} preferably an alkylene group.

m represents an integer of 2 or more, preferably 2-20, more preferably 2-10.

The substituent that the alkyl group, aryl group, and heteroaryl group may have is preferably a group having a branched alkyl structure. In addition, the substituent is preferably a hydrocarbon group that may contain an oxygen atom, and more preferably a hydrocarbon group that contains an oxygen atom. The hydrocarbon group containing an oxygen atom is preferably a group represented by ^{-OR x1.} R ^{x1 is} preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and particularly preferably a branched alkyl group. That is, the substituent is more preferably an alkoxy group, and particularly preferably a branched alkoxy group. When the substituent is an alkoxy group, it is easy to obtain a film having excellent heat resistance and light resistance. The carbon number of the alkoxy group is preferably 1-40. The lower limit is, for example, more preferably 3 or more, still more preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The alkoxy group may be any of linear, branched, and cyclic, preferably linear or branched, and particularly preferably branched. The carbon number of the branched alkoxy group is preferably 3-40. The lower limit is, for example, more preferably 5 or more, still more preferably 8 or more, and still more preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The number of branches of the branched alkoxy group is preferably 2-10, more preferably 2-8.

As ^{specific examples of C 1} and C ² , the following can be cited. In the following, Me represents a methyl group, and Bu represents a butyl group. * Indicates the bonding position with formula (I). In addition, the following optical isomers can also be preferably used.

[化10]

In formula (I), D ¹ and D ² each independently represent a substituent. D ¹ and D ² may be the same group or different groups. D ¹ and D ^{2 are} preferably the same group.

Examples of substituents include alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, and heteroaryloxy. Carbonyl group, acyloxy group, amine group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heteroaryloxycarbonylamino group, sulfonylamino group, sulfamoylamino group, sulfamoyl group, carbamate Acetyl, alkylthio, arylthio, heteroarylthio, alkylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylsulfinyl, arylsulfinyl, hetero Arylsulfinyl group, ureido group, phosphoamido group, mercapto group, sulfo group, carboxyl group, nitro group, hydroxyl amino acid group, sulfinic acid group, hydrazine group, imino group, silyl group, hydroxyl group, halogen atom, cyanide Base and so on. D ¹ and D ^{2 are} preferably electron withdrawing groups.

The substituent whose substituent constant σ _p value (sigma para value) of Hammett is positive functions as an electron withdrawing group. In the present invention, _{a substituent having Hammett's σ p} value of 0.2 or more can be exemplified as the electron withdrawing group. The σ _p value is preferably 0.25 or more, more preferably 0.3 or more, and particularly preferably 0.35 or more. The upper limit is not particularly limited, but it is preferably 0.80 or less. Specific examples of electron withdrawing groups include: cyano (0.66), carboxyl (-COOH: 0.45), alkoxycarbonyl (for example, -COOMe: 0.45), and aryloxycarbonyl (for example, -COOPh: 0.44) , Carboxamide (for example, -CONH ₂ : 0.36), alkylcarbonyl (for example, -COMe: 0.50), arylcarbonyl (for example, -COPh: 0.43), alkylsulfonyl (for example, -SO ₂ Me: 0.72), arylsulfonyl (for example, -SO ₂ Ph: 0.68), and the like. Preferred are cyano, alkylcarbonyl, alkylsulfonyl and arylsulfonyl, and more preferred is cyano. Here, Me represents a methyl group, Ph represents a phenyl group, and the value in parentheses is the σ _p value. Regarding the σ _p value of Hammett, reference can be made to paragraph numbers 0024 to 0025 of JP 2009-263614 A, and this content is incorporated into this specification.

As ^{specific examples of D 1} and D ² , the following can be cited. * Indicates the bonding position with formula (I).

The pyrrolopyrrole compound is preferably a compound represented by the following formula (II) or a compound represented by the following formula (III). According to this aspect, it is easy to form a pattern excellent in infrared shielding properties and light resistance.

In formula (II), X ¹ and X ² each independently represent O, S, NR ^X1 or CR ^X2 R ^X3 , R ^X1 to R ^X3 each independently represent a hydrogen atom or a substituent, and R ³ to R ⁶ each independently Represents a hydrogen atom or a substituent, R ³ and R ⁴ , or R ⁵ and R ⁶ may be bonded to each other to form a ring, B ¹ and B ² each independently represent a -BR ¹ R ² group, and R ¹ and R ² are each independent Represents a substituent, R ¹ and R ² may be bonded to each other to form a ring, C ¹ and C ² each independently represent an alkyl group, an aryl group, or a heteroaryl group, and D ¹ and D ² each independently represent a substituent.

B of formula (II) is ^{1, B 2, C 1,} C 2, B D 1 and D meaning as in formula (I) is ² to ^{1, B 2, C 1,} C 2, the same ^{D. 1} and D ^2, more The optimal range is also the same. ^{X 1} , X ² and R ³ to R ⁶ in formula (II) have ^{the same meanings as X 1} , R ³ and R ^{4 in} formula (A-1), and the preferred ranges are also the same.

In formula (III), Y ¹ to Y ⁸ independently represent N or CR ^Y1 , at least two of ^{Y 1} to Y ^{4 are CR Y1} , ^{at least two of Y 5} to Y ⁸ are CR ^Y1 , and R ^Y1 represents hydrogen Atoms or substituents, adjacent R ^Y1 may bond to each other to form a ring, B ¹ and B ² each independently represent a -BR ¹ R ² group, R ¹ and R ² each independently represent a substituent, R ¹ and R ² may be bonded to each other to form a ring, C ¹ and C ² each independently represent an alkyl group, an aryl group, or a heteroaryl group, and D ¹ and D ² each independently represent a substituent.

B of formula (III) is ^{1, B 2, C 1,} C 2, B D 1 and D meaning as in formula (I) is ² to ^1, B ^2, C ^1, same as C ^2, D ¹ and D ^2, more The optimal range is also the same. ^{The meanings of Y 1} to Y ⁸ in the formula (III) are the ^{same as those of Y 1} to Y ^{4 in} the formula (A-2), and the preferred ranges are also the same.

As specific examples of the pyrrolopyrrole compound, the following compounds can be cited. In the following structural formulas, Ph represents a phenyl group, Me represents a methyl group, and Bu represents a butyl group. In addition, as specific examples of the pyrrolopyrrole compound, the compounds described in paragraph number 0049 to paragraph number 0058 of JP 2009-263614 A can also be cited, and this content is incorporated in this specification.

[化13]

(Squaraine ylide compound)

In the present invention, the squaraine ylide compound is preferably a compound represented by the following formula (1). The following compounds are preferably compounds having the aforementioned absorbance ratio.

In formula (1), A ¹ and A ² each independently represent an aryl group, a heteroaryl group, or a group represented by the following general formula (2);

In the formula (2), Z ¹ represents a non-metal atomic group forming a nitrogen-containing heterocyclic ring, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and a wavy line represents a bond with the formula (1).

^{A 1} and A ² in the formula (1) each independently represent an aryl group, a heteroaryl group, or a group represented by the formula (2), and are preferably a group represented by the formula (2).

The carbon number of the aryl group represented by A ¹ and A ² is preferably 6 to 48, more preferably 6 to 24, and particularly preferably 6 to 12. As a specific example, a phenyl group, a naphthyl group, etc. are mentioned.

The heteroaryl group represented by A ¹ and A ² is preferably a 5-membered ring or a 6-membered ring. In addition, the heteroaryl group is preferably a monocyclic ring or a condensed ring, and is preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 8, more preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 4, and more preferably A single ring or a condensed ring with a condensation number of 2 or 3. As the hetero atom contained in the heterocyclic group, a nitrogen atom, an oxygen atom, and a sulfur atom can be exemplified, and a nitrogen atom and a sulfur atom are preferable. The number of heteroatoms is preferably 1-3, more preferably 1-2. Specifically, a heteroaryl group derived from a monocyclic or polycyclic aromatic ring such as a 5-membered ring or a 6-membered ring containing at least one of a nitrogen atom, an oxygen atom, and a sulfur atom, etc. can be cited.

The aryl group and heteroaryl group may have a substituent. When the aryl group and the heteroaryl group have two or more substituents, a plurality of substituents may be the same or different.

Examples of substituents include halogen atoms, cyano groups, nitro groups, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, aralkyl groups, -OR ¹⁰ , -COR ¹¹ , -COOR ¹² , and -OCOR ¹³ , -NR ¹⁴ R ¹⁵ , -NHCOR ¹⁶ , -CONR ¹⁷ R ¹⁸ , -NHCONR ¹⁹ R ²⁰ , -NHCOOR ²¹ , -SR ²² , -SO ₂ R ²³ , -SO ₂ OR ²⁴ , -NHSO ₂ R ²⁵ or -SO ₂ NR ²⁶ R ²⁷ . R ¹⁰ to R ²⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. Furthermore, in the case where R ^{12 of -COOR 12} is a hydrogen atom (that is, a carboxyl group), the hydrogen atom may be dissociated and may be in the state of a salt. In addition, when R ²⁴ _{of -SO 2} OR ²⁴ is a hydrogen atom (that is, a sulfo group), the hydrogen atom may be dissociated or may be in the form of a salt.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The carbon number of the alkyl group is preferably 1-20, more preferably 1-15, and still more preferably 1 ~8. The alkyl group may be any of linear, branched, and cyclic, and is preferably linear or branched.

The carbon number of the alkenyl group is preferably 2-20, more preferably 2-12, particularly preferably 2-8. The alkenyl group may be any of linear, branched, and cyclic, and is preferably linear or branched.

The carbon number of the alkynyl group is preferably 2-40, more preferably 2-30, particularly preferably 2-25. The alkynyl group may be linear, branched, and cyclic, and is preferably linear or branched.

The carbon number of the aryl group is preferably 6-30, more preferably 6-20, and still more preferably 6-12.

The alkyl part of the aralkyl group is the same as the alkyl group. The aryl part of the aralkyl group is the same as the aryl group. The carbon number of the aralkyl group is preferably 7-40, more preferably 7-30, and still more preferably 7-25.

The heteroaryl group is preferably a monocyclic ring or a condensed ring, and is preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 8, more preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 4. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1-3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3-30, more preferably 3-18, and still more preferably 3-12.

The alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, and heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include the above-mentioned substituents.

Next, the group represented by the formula (2) represented by ^{A 1} and A ^{2 will be described.}

In the formula (2), R ² represents an alkyl group, an alkenyl group or an aralkyl group, preferably an alkyl group.

The carbon number of the alkyl group is preferably 1-30, more preferably 1-20, still more preferably 1-12, particularly preferably 2-8.

The carbon number of the alkenyl group is preferably 2-30, more preferably 2-20, and still more preferably 2-12.

The alkyl group and the alkenyl group may be linear, branched, and cyclic, and are preferably linear or branched.

The carbon number of the aralkyl group is preferably 7-30, more preferably 7-20.

In formula (2), ^{the nitrogen-containing heterocyclic ring formed by Z 1 is} preferably a 5-membered ring or a 6-membered ring. In addition, the nitrogen-containing heterocyclic ring is preferably a monocyclic ring or a condensed ring, and is preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 8, more preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 4, and still more Preferred is a condensed ring having a condensation number of 2 or 3. The nitrogen-containing heterocyclic ring may contain a sulfur atom in addition to the nitrogen atom. In addition, the nitrogen-containing heterocyclic ring may have a substituent. Examples of the substituent include the above-mentioned substituents. For example, a halogen atom, an alkyl group, a hydroxyl group, an amino group, and an acylamino group are preferable, and a halogen atom and an alkyl group are more preferable. The halogen atom is preferably a chlorine atom. The carbon number of the alkyl group is preferably 1-30, more preferably 1-20, and still more preferably 1-12. The alkyl group is preferably linear or branched.

The group represented by the formula (2) is preferably a group represented by the following formula (3) or (4).

[化21]

In formulas (3) and (4), R ¹¹ represents an alkyl group, an alkenyl group or an aralkyl group, R ¹² represents a substituent, and when m is 2 or more, R ¹² can be linked to each other to form a ring, and X represents Nitrogen atom or CR ¹³ R ¹⁴ , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent, m represents an integer of 0 to 4, and a wavy line represents a bond with formula (1).

^{The meaning of R 11} in formula (3) and formula (4) is the ^{same as that of R 2} in formula (2), and the preferred range is also the same.

^{R 12 in} formula (3) and formula (4) represents a substituent. As a substituent, the substituent demonstrated in the said formula (1) is mentioned. For example, a halogen atom, an alkyl group, a hydroxyl group, an amino group, and an acylamino group are preferable, and a halogen atom and an alkyl group are more preferable. The halogen atom is preferably a chlorine atom. The carbon number of the alkyl group is preferably 1-30, more preferably 1-20, and still more preferably 1-12. The alkyl group is preferably linear or branched.

When m is 2 or more, R ¹² can be connected to each other to form a ring. Examples of the ring include an alicyclic ring (non-aromatic hydrocarbon ring), aromatic ring, heterocyclic ring, and the like. The ring can be a single ring or multiple rings. As the linking group when the substituents are connected to each other to form a ring, there may be selected from -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, a divalent unsaturated chain hydrocarbon group, and the The divalent linking group in the group formed by the combination of these. For example, it is preferable that R ¹² are connected to each other to form a benzene ring.

X in the formula (3) represents a nitrogen atom or CR ¹³ R ¹⁴ , and R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent. As a substituent, the substituent demonstrated in the said formula (1) is mentioned. For example, an alkyl group etc. can be mentioned. The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, further preferably from 1 to 5, particularly preferably from 1 to 3, and most preferably from 1. The alkyl group is preferably linear or branched, particularly preferably linear.

m represents an integer of 0-4, preferably 0-2.

In addition, in formula (1), cations exist in a non-localized manner as follows.

The squaraine ylide dye is preferably a compound represented by the following formula (5).

Rings A and B each independently represent an aromatic ring or a heteroaromatic ring, X ^A and X ^B each independently represent a substituent group, G ^A and G ^B independently represents a substituent group, kA represents 0 to an integer of nA, kB represents An integer from 0 to nB, nA and nB respectively represent the largest integers that can be substituted in ring A or ring B. X ^A and G ^A , X ^B and G ^B can be bonded to each other to form a ring, which exists ^{in G A} and G ^{B respectively} In the case of a plurality of them, they may be bonded to each other to form a ring structure.

G ^A and G ^B independently represents a substituent group. As a substituent, the substituent demonstrated in the said formula (1) is mentioned.

X ^A and X ^B each independently represent a substituent. Examples of the substituent include the substituents described in the formula (1), preferably having active hydrogen, more preferably -OH, -SH, -COOH, -SO ₃ H, -NR ^X1 R ^X2 , -NHCOR ^X1 , -CONR ^X1 R ^X2 , -NHCONR ^X1 R ^X2 , -NHCOOR ^X1 , -NHSO ₂ R ^X1 , -B(OH) ₂ and -PO(OH) ₂ , more preferably -OH, -SH and -NR ^X1 R ^X2 .

R ^X1 and R ^X2 each independently represent a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and an alkyl group is preferred. The alkyl group is preferably linear or branched. The details of the alkyl group, alkenyl group, alkynyl group, aryl group, and heteroaryl group are the same as those described in the column of the substituent.

Ring A and ring B each independently represent an aromatic ring or a heteroaromatic ring.

The aromatic ring and heteroaromatic ring may be a single ring or a condensed ring.

環、三伸苯環、茀環、聯苯環、吡咯環、呋喃環、噻吩環、咪唑環、噁唑環、噻唑環、吡啶環、吡嗪環、嘧啶環、噠嗪環、吲哚嗪環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹嗪環、喹啉環、酞嗪環、萘啶環、喹噁啉環、喹噁唑啉環、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉環、噻蒽環、苯并哌喃環、呫噸環、啡噁噻環、啡噻嗪環及啡嗪環，較佳為苯環或萘環。 Specific examples of aromatic rings and heteroaromatic rings include benzene ring, naphthalene ring, pentene ring, indene ring, azulene ring, heptene ring, benzobiindene ring, perylene ring, fused pentabenzene ring, Acenaphthene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring,

Ring, trimethylene ring, pyridine ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indoleazine Ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, iso Quinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthracene ring, benzopyran ring, xanthene ring, phenoxathi ring, phenanthrazine ring and phenanthrazine ring, preferably It is a benzene ring or a naphthalene ring.

The aromatic ring may be unsubstituted or may have a substituent. As a substituent, the substituent demonstrated in the said formula (1) is mentioned.

X ^A and G ^A, X ^B and G ^B may be bonded to each other to form a ring to form a ring, G ^A and G ^B in the case where there are a plurality of, may be bonded to each other.

The ring is preferably a 5-membered ring or a 6-membered ring. The ring can be a single ring or multiple rings.

When X ^A and G ^A , X ^B and G ^B , G ^A or G ^B are bonded to each other to form a ring, these may be directly bonded to form a ring, or may be selected from alkylene, -CO The divalent linking group in the group consisting of -, -O-, -NH-, -BR- and combinations of these bonds to form a ring. Preferably, X ^A and G ^A , X ^B and G ^B , G ^A or G ^B are bonded to each other via -BR- to form a ring.

R represents a hydrogen atom or a substituent. Examples of the substituent include the substituents described in the above formula (1), and an alkyl group or an aryl group is preferred.

kA represents an integer from 0 to nA, kB represents an integer from 0 to nB, nA represents the largest integer that can be substituted for the A ring, and nB represents the largest integer that can be substituted for the B ring.

kA and kB are preferably 0-4 independently of each other, more preferably 0-2, particularly preferably 0 ~1.

As an embodiment of the squarylium ylide dye, a compound represented by the following formula (6) can be cited. The compound has excellent heat resistance.

In the formula, R ¹ and R ² each independently represent a substituent, R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group, and X ¹ and X ² each independently represent -O- or -N (R ⁵ )-, R ⁵ represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, Y ¹ to Y ⁴ each independently represent a substituent, and Y ¹ and Y ² , and Y ³ and Y ⁴ can also be formed by bonding to each other Ring, Y ¹ ~ Y ⁴ may be bonded to each other to form a ring when there are multiple, respectively, p and s each independently represent an integer from 0 to 3, and q and r each independently represent an integer from 0 to 2 .

Examples of the substituents represented by R ¹ , R ² , and Y ¹ to Y ⁴ include the substituents described in the above formula (1).

R ³ and R ^{4 are} preferably each independently a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

X ¹ and X ² each independently represent -O- or -N(R ⁵ )-. X ¹ and X ² may be the same or different, and are preferably the same.

R ⁵ represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.

R ^{5 is} preferably a hydrogen atom, an alkyl group or an aryl group. The alkyl group, aryl group, and heteroaryl group represented by R ^{5 may be unsubstituted or may have a substituent.} As a substituent, the substituent demonstrated in the said formula (1) is mentioned.

The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, further preferably from 1 to 4, and particularly preferably from 1 to 2. The alkyl group may be either linear or branched.

The carbon number of the aryl group is preferably 6-20, more preferably 6-12.

Heteroaryl groups may be monocyclic or polycyclic. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1-3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3-30, more preferably 3-18, and still more preferably 3-12.

As a specific example of a squarylium ylide compound, the compound shown below can be mentioned. In addition, the compounds described in paragraph number 044 to paragraph number 0049 of JP 2011-208101 A can be cited, and the content is incorporated in this specification.

[化25]

(Cyanine compound)

In the present invention, the cyanine compound is preferably a compound represented by the following formula (C). The following compounds are preferably compounds having the aforementioned absorbance ratio.

Formula (C) [化26]

In the formula (C), Z ¹ and Z ² are each independently a non-metallic atomic group forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring that forms a condensable ring, and R ¹⁰¹ and R ¹⁰² each independently represent an alkyl group, an alkenyl group, Alkynyl, aralkyl, or aryl, L ¹ represents a methine chain with an odd number of methine groups, a and b are each independently 0 or 1, and when a is 0, the carbon atom and the nitrogen atom It is bonded by a double bond. When b is 0, the carbon atom and the nitrogen atom are bonded by a single bond. When the part represented by Cy in the formula is a cation part, X ¹ represents an anion, and c It represents the number required to balance the charge. In the case where the part represented by Cy in the formula is the anion part, X ¹ represents a cation, and c represents the number required to balance the charge. When the electric charge at the part represented by Cy in the formula is neutralized in the molecule, c is zero.

In the formula (C), Z ¹ and Z ² each independently represent a non-metal atomic group forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring that forms a condensable ring. In the nitrogen-containing heterocycle, other heterocycles, aromatic rings or aliphatic rings may also be condensed. The nitrogen-containing heterocyclic ring is preferably a 5-membered ring. Furthermore, a structure in which a benzene ring or a naphthalene ring is condensed to a 5-membered nitrogen-containing heterocyclic ring is preferable. Specific examples of nitrogen-containing heterocycles include: oxazole ring, isoxazole ring, benzoxazole ring, naphthoxazole ring, oxazocarbazole ring, oxazolodibenzofuran ring, thiazole Ring, benzothiazole ring, naphthiazole ring, indole ring, benzoindole ring, imidazole ring, benzimidazole ring, naphthimidazole ring, quinoline ring, pyridine ring, pyrrolopyridine ring, fluorine Pyrrole ring, indoleazine ring, imidazoquinoxaline ring, quinoxaline ring, etc., preferably quinoline ring, indole ring, benzoindole ring, benzoxazole ring, benzothiazole ring , Benzimidazole ring, particularly preferably indole ring, benzothiazole ring, and benzimidazole ring. The nitrogen-containing heterocyclic ring and the ring condensed thereon may have a substituent. As a substituent, the substituent demonstrated in Formula (1) can be mentioned.

In formula (C), R ¹⁰¹ and R ¹⁰² each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group.

The carbon number of the alkyl group is preferably 1-20, more preferably 1-12, and particularly preferably 1-8. The alkyl group may be any of linear, branched, and cyclic.

The carbon number of the alkenyl group is preferably 2-20, more preferably 2-12, particularly preferably 2-8. The alkenyl group may be any of linear, branched, and cyclic.

The carbon number of the alkynyl group is preferably 2-20, more preferably 2-12, and particularly preferably 2-8. The alkynyl group may be any of linear, branched, and cyclic.

The carbon number of the aryl group is preferably 6-25, more preferably 6-15, most preferably 6-10. The aryl group may be unsubstituted or may have a substituent.

The alkyl part of the aralkyl group is the same as the alkyl group. The aryl part of the aralkyl group is the same as the aryl group. The carbon number of the aralkyl group is preferably 7-40, more preferably 7-30, and still more preferably It is 7~25.

The alkyl group, alkenyl group, alkynyl group, aralkyl group, and aryl group may have a substituent or may be unsubstituted. As a substituent, a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an amino group, etc. are mentioned, A carboxyl group and a sulfo group are preferable, and a sulfo group is especially preferable. The hydrogen atoms of the carboxyl group and the sulfo group may be dissociated, or may be in the form of a salt.

In formula (C), L ¹ represents a methine chain having an odd number of methine groups. L ^{1 is} preferably a methine chain having 3, 5 or 7 methine groups.

The methine group may have a substituent. The substituted methine group is preferably a central (meta) methine group. As a specific example of ^{a substituent, the substituent which the nitrogen-containing heterocyclic ring of Z 1} and Z ² may have, the group represented by following formula (a), etc. are mentioned. In addition, the two substituents of the methine chain may be bonded to form a 5-membered ring or a 6-membered ring.

In the formula (a), * represents a connection part with a methine chain, and A ¹ represents -O-.

In formula (C), a and b are independently 0 or 1, respectively. When a is 0, the carbon atom and the nitrogen atom are bonded by a double bond, and when b is 0, the carbon atom and the nitrogen atom are bonded by a single bond. Both a and b are preferably 0. In addition, when both a and b are 0, the formula (C) is expressed as follows.

In the formula (C), when the part represented by Cy in the formula is a cationic part, X ¹ represents an anion, and c represents the number required to balance the charges. Examples of the anions include: halide ions ^{(Cl -, Br -, I} -), p-toluenesulfonate ion, ethyl sulfate _{^{ion, PF 6 -, BF 4 -}} , ClO 4 -, tris (haloalkyl sulfo acyl) methide anion _{(e.g., (CF 3 SO 2) 3} C -), bis (sulfo-haloalkyl acyl) acyl imide anion (e.g. _{(CF 3 SO 2) 2 N} -), tetracyanoquinodimethane Borate anions and so on.

In the formula (C), when the part represented by Cy in the formula is an anion part, X ¹ represents a cation, and c represents the number required to balance the charges. Examples of cations include alkali metal ions (Li ⁺ , Na ⁺ , K ^+, etc.), alkaline earth metal ions (Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Sr ^2+, etc.), transition metal ions (Ag ⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ²⁺ etc.), other metal ions (Al ³⁺ etc.), ammonium ion, triethylammonium ion, tributylammonium ion, pyridinium ion , Tetrabutylammonium ion, guanidinium ion, tetramethylguanidinium ion, diazabicycloundecenium ion, etc. The cation is preferably Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Zn ²⁺ , diazabicycloundecenium ion.

In the formula (C), when the electric charge at the site represented by Cy in the formula is neutralized in the molecule, X ¹ does not exist. That is, c is 0.

The cyanine compound is also preferably represented by the following formula (C-1) ~ formula (C-3) compound of.

In the formula, R ^1A , R ^2A , R ^1B and R ^2B each independently represent an alkyl, alkenyl, alkynyl, aralkyl or aryl group, and L ^1A and L ^1B each independently represent an odd number of methine groups Methylene chain, Y ¹ and Y ² each independently represent -S-, -O-, -NR ^X1 -or -CR ^X2 R ^X3 -, R ^X1 , R ^X2, and R ^X3 each independently represent a hydrogen atom or an alkane Group, V ^1A , V ^2A , V ^1B and V ^2B each independently represent a substituent, m1 and m2 each independently represent 0 to 4, and when the part represented by Cy in the formula is a cationic part, X ¹ represents Anion, c represents the number required to balance the charge. In the case where the part represented by Cy in the formula is the anion part, X ¹ represents a cation, and c represents the number required to balance the charge When the electric charge at the site represented by Cy in the formula is neutralized in the molecule, X ¹ does not exist.

The meanings of the groups represented by R ^1A , R ^2A , R ^1B and R ^2B are the same as the alkyl, alkenyl, alkynyl, aralkyl and aryl groups described in ^{R 101} and R ^{102 of formula (C), preferably} The scope is also the same. These groups may be unsubstituted or substituted. As a substituent, a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an amine group, etc. are mentioned, A carboxyl group and a sulfo group are preferable, and a sulfo group is especially preferable. The hydrogen atoms of the carboxyl group and the sulfo group may be dissociated, or may be in the form of a salt. When R ^1A , R ^2A , R ^1B and R ^2B represent an alkyl group, it is more preferably a linear alkyl group.

Y ¹ and Y ² each independently represent -S-, -O-, -NR ^X1 -or -CR ^X2 R ^X3 -, preferably -NR ^X1 -. R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom or an alkyl group, and an alkyl group is preferred. The carbon number of the alkyl group is preferably from 1 to 10, more preferably from 1 to 5, and particularly preferably from 1 to 3. The alkyl group may be any of linear, branched, and cyclic, preferably linear or branched, and particularly preferably linear. The alkyl group is particularly preferably a methyl group or an ethyl group.

The meanings of L ^1A and L ^{1B are the same as L 1 in} formula (C), and the preferred ranges are also the same.

Examples of the substituents represented by V ^1A , V ^2A , V ^1B and V ^2B include the above-mentioned substituents, and the preferred ranges are also the same.

m1 and m2 each independently represent 0-4, preferably 0-2.

Cation and the anion of formula X (C) ¹ X ¹ in the same range as indicated below, preferred ranges are also the same.

As a specific example of a cyanine compound, the compound shown below can be mentioned. In addition, the compounds described in Japanese Patent Laid-Open No. 2015-172004 and Japanese Patent Laid-Open No. 2015-172102 can be cited.

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(Other near-infrared absorbing compounds)

The near-infrared absorbing agent may further include near-infrared absorbing compounds (also referred to as other near-infrared absorbing compounds) other than the near-infrared absorbing compound A.

Other near-infrared absorbing compounds may be pigments or dyes. Since it is easy to form a pattern excellent in rectangularity, a pigment is preferable. In addition, the pigment may be an inorganic pigment or an organic pigment.

Examples of other near-infrared absorbing compounds include phthalocyanine compounds, naphthalocyanine compounds, perylene compounds, merocyanine compounds, crotonium compounds, oxonine compounds, diiminium compounds, dithiol compounds, and triaryl groups. Methane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, etc. As a phthalocyanine compound, a phthalocyanine titanyl pigment etc. are mentioned. In addition, the phthalocyanine compound, the naphthalocyanine compound, the diiminium compound, and the croconium compound can also use the compounds disclosed in paragraph number 0010 to paragraph number 0081 of JP 2010-111750 A, and this content is incorporated. To this manual. In addition, IRA868 (manufactured by Exiton), IRG-068 (manufactured by Nippon Kayaku Co., Ltd.), etc. can also be used.

In addition, as other near-infrared absorbing compounds, inorganic pigments may also be used. In terms of more excellent infrared shielding properties, the inorganic pigment is preferably metal oxide particles or metal particles. Examples of metal oxide particles include: indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO) particles, and aluminum-doped zinc oxide (Al-doped ZnO) particles. ) Particles, fluorine-doped tin dioxide (F-doped SnO ₂ ) particles, niobium-doped titanium dioxide (Nb-doped TiO ₂ ) particles, etc. Examples of metal particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, nickel (Ni) particles, and the like. The shape of the inorganic pigment is not particularly limited, and is not limited to a spherical shape or a non-spherical shape, and may be a flake shape, a linear shape, or a tube shape.

In addition, as the inorganic pigment, a tungsten oxide-based compound may also be used. Specifically, a tungsten oxide-based compound represented by the following formula (W-1) is preferred.

M _x W _y O _z . . . (W-1)

M represents metal, W represents tungsten, and O represents oxygen.

0.001≦x/y≦1.1 2.2≦z/y≦3.0

Examples of metals represented by M include alkali metals, alkaline earth metals, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi are preferably alkali metals, more preferably Rb or Cs, particularly preferably Cs. The metal of M may be one type or two or more types.

When x/y is 0.001 or more, infrared rays can be sufficiently shielded, and when x/y is 1.1 or less, it is possible to more reliably avoid the generation of impurity phases in the tungsten oxide compound.

When z/y is 2.2 or more, the chemical stability of the material can be further improved, and when z/y is 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of tungsten oxide compounds include: Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _3, etc., preferably Cs _0.33 WO ₃ or Rb _0.33 WO ₃ , and more preferably Cs _0.33 WO ₃ .

The tungsten oxide-based compound can be obtained as a dispersion of tungsten fine particles such as YMF-02 and YMS-01A-2 manufactured by Sumitomo Metal Mining Co., Ltd., for example.

The average particle diameter of the inorganic pigment is preferably 800 nm or less, more preferably 400 nm or less, and still more preferably 200 nm or less. When the average particle diameter of the inorganic pigment is in this range, the light transmittance in the visible light region can be made more reliable. From the viewpoint of avoiding light scattering, the smaller the average particle size is, the better, but for reasons such as ease of handling during production, the lower limit of the average particle size of the inorganic pigment is 1 nm or more.

When the near-infrared absorbing agent contains other near-infrared absorbing compounds, the content of the other near-infrared absorbing compounds is preferably 0.1 to 80 parts by mass, more preferably 5 parts by mass relative to 100 parts by mass of the near-infrared absorbing compound A Parts to 60 parts by mass, more preferably 10 parts by mass to 40 parts by mass.

<<Color Colorant>>

The composition of the present invention may contain a coloring agent. In the present invention, the term "color coloring agent" refers to coloring agents other than white coloring agent and black coloring agent. The coloring agent is preferably a coloring agent that has absorption in the range of 400 nm or more and less than 650 nm in wavelength. In the present invention, the coloring agent may be a pigment or a dye.

The pigment is preferably an organic pigment, and the following can be cited. However, the pigments that can be used in the present invention are not limited to these.

Dye Index (Colour Index, CI) Pigment Yellow 1, CI Pigment Yellow 2, CI Pigment Yellow 3, CI Pigment Yellow 4, CI Pigment Yellow 5, CI Pigment Yellow 6, CI Pigment Yellow 10, CI Pigment Yellow 11 , CI Pigment Yellow 12, CI Pigment Yellow 13. CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 18, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 32, CI Pigment Yellow 34. CI Pigment Yellow 35, CI Pigment Yellow 35:1, CI Pigment Yellow 36, CI Pigment Yellow 36:1, CI Pigment Yellow 37, CI Pigment Yellow 37:1, CI Pigment Yellow 40, CI Pigment Yellow 42, CI Pigment Yellow 43, CI Pigment Yellow 53, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 62, CI Pigment Yellow 63, CI Pigment Yellow 65, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 77, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 115, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 118, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 123, CI Pigment Yellow 125, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 161, CI Pigment Yellow 162, CI Pigment Yellow 164, CI Pigment Yellow 166, CI Pigment Yellow 167, CI Pigment Yellow 168, CI Pigment Yellow 169, CI Pigment Yellow 170, CI Pigment Yellow 171, CI Pigment Yellow 172, CI Pigment Yellow 173, CI Pigment Yellow 174, CI Pigment Yellow 175, CI Pigment Yellow 176, CI Pigment Yellow 177, CI Pigment Yellow 179, CI Pigment Yellow 180, CI Pigment Yellow 181, CI Pigment Yellow 182, CI Pigment Yellow 185, CI Pigment Yellow 187, CI Pigment Yellow 188, CI Pigment Yellow 193, CI Pigment Yellow 194, CI Pigment Yellow 199, CI Pigment Yellow 213, CI Pigment Yellow 214, etc. (the above are yellow pigments), CI Pigment Orange (Pigment Orange)2, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 16, CI Pigment Orange 17:1, CI Pigment Orange 31, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 48, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 52, CI Pigment Orange 55, CI Pigment Orange 59, CI Pigment Orange 60, CI Pigment Orange 61, CI Pigment Orange 62, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, etc. (the above are orange pigments), CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 14, CI Pigment Red 17, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 31, CI Pigment Red 38, CI Pigment Red 41, CI Pigment Red 48:1, CI Pigment Red 48: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49, CI Pigment Red 49:1, CI Pigment Red 49:2, CI Pigment Red 52:1, CI Pigment Red 52:2, CI Pigment Red 53:1, CI Pigment Red 57:1, CI Pigment Red 60:1, CI Pigment Red 63:1, CI Pigment Red 66, CI Pigment Red 67, CI Pigment Red 81:1, CI Pigment Red 81: 2, CI Pigment Red 81: 3, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90, CI Pigment Red 105, CI Pigment Red 112, CI Pigment Red 119, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red Material Red 150, CI Pigment Red 155, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 169, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 184, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 200, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 210, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 246, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 270, CI Pigment Red 272, CI Pigment Red 279, etc. (the above are red pigments), CI Pigment Green 7. CI Pigment Green 10, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Green 58, CI Pigment Green 59, etc. (the above are green pigments), CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23 , CI Pigment Violet 27, CI Pigment Violet 32, CI Pigment Violet 37, CI Pigment Violet 42, etc. (the above are purple pigments), CI Pigment Blue 1, CI Pigment Blue 2, CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64. CI Pigment Blue 66, CI Pigment Blue 79, CI Pigment Blue 80, etc. (the above are blue pigments).

These organic pigments can be used alone or in combination of various organic pigments.

The dye is not particularly limited, and known dyes can be used. As the chemical structure, pyrazole azo series, anilino azo series, triphenylmethane series, anthraquinone series, anthrapyridone series, benzylidene series, oxacyanine series, pyrazolotriazole series can be used. Nitrogen series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole azomethine series, xanthene series, phthalocyanine series, benzopyran series, indigo series, pyrrole Dyes such as methylene series. In addition, multimers of these dyes can also be used. In addition, the dyes described in Japanese Patent Laid-Open No. 2015-028144 and Japanese Patent Laid-Open No. 2015-34966 can also be used.

<<Colored material that transmits at least a part of light in the infrared region and shields light in the visible region (colored material that shields visible light)>>

The composition of the present invention may also contain a colored material that transmits at least a part of light in the infrared region and shields light in the visible region (hereinafter, also referred to as a colored material that shields visible light).

The colored material that shields visible light preferably satisfies at least one of the following requirements (1) and (2), and more preferably satisfies the requirement (1).

(1): An aspect containing two or more color colorants.

(2): An aspect containing an organic black colorant.

<<Pigment Derivatives>>

When the composition of the present invention contains a pigment, it may further contain a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of the pigment is substituted with an acidic group, a basic group, or a phthaliminomethyl group, and more preferably a pigment derivative represented by the following formula (B1) .

In formula (B1), P represents a dye structure, L represents a single bond or a linking group, X represents an acidic group, a basic group, a group having a salt structure, or a phthalimide group, and m represents an integer of 1 or more, n represents an integer of 1 or more, and when m is 2 or more, a plurality of L and X may be the same as or different from each other, and when n is 2 or more, a plurality of X may be the same or different from each other.

In formula (B1), P represents a pigment structure, preferably selected from the group consisting of pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, quinacridone pigment structure, anthraquinone pigment structure, dianthraquinone pigment structure, benzene Diisoindole pigment structure, thiazide indigo pigment structure, azo pigment structure, quinophthalone pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, dioxazine pigment structure, perylene pigment structure, perylene pigment structure , At least one of benzimidazolone pigment structure, benzothiazole pigment structure, benzimidazole pigment structure and benzoxazole pigment structure, and more preferably selected from pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure , At least one of quinacridone pigment structure and benzimidazolone pigment structure, particularly preferably pyrrolopyrrole pigment structure.

In addition, the dye structure represented by P is preferably a dye structure derived from a near-infrared absorbing compound, and more preferably a dye structure having a skeleton common to the near-infrared absorbing compound contained in the near-infrared absorbing agent. For example, in the case of using a pyrrolopyrrole compound as a near-infrared absorbing compound, the pigment structure represented by P is preferably pyrrole The structure of pyrrole pigment.

In the formula (B1), L represents a single bond or a linking group. The linking group is preferably a group including 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. Substitution may further have a substituent.

In the formula (B1), X represents an acidic group, a basic group, a group having a salt structure, or a phthalimide group.

As specific examples of pigment derivatives, the following compounds can be cited. In addition, Japanese Patent Laid-Open No. 56-118462, Japanese Patent Laid-Open No. 63-264674, Japanese Patent Laid-Open No. 1-217077, Japanese Patent Laid-Open No. 3-9961, and Japanese Patent Kaihei No. 3-26767, Japanese Patent Laid-open No. 3-153780, Japanese Patent Laid-Open No. 3-45662, Japanese Patent Laid-Open No. 4-285669, Japanese Patent Laid-Open No. 6-145546, Japanese Patent Japanese Patent Publication No. 6-212088, Japanese Patent Publication No. 6-240158, Japanese Patent Publication No. 10-30063, Japanese Patent Publication No. 10-195326, International Publication No. WO2011/024896, paragraph numbers 0086~paragraphs No. 0098, Paragraph No. 0063 to Paragraph No. 0094 of International Publication WO2012/102399 Handbook, etc., are incorporated into this specification.

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When the composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 part by mass to 50 parts by mass relative to 100 parts by mass of the pigment contained in the composition. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less. If the content of the pigment derivative is in the above range, the dispersibility of the pigment can be improved, and the aggregation of particles can be efficiently suppressed. There may be only one type of pigment derivative, or two or more types. In the case of two or more types, the total amount is preferably within the above range.

<<radical polymerizable compound>>

The composition of the present invention contains a radical polymerizable compound (hereinafter also referred to as a polymerizable compound). The polymerizable compound is not particularly limited as long as it is a compound that can be polymerized by the action of radicals. The polymerizable compound is preferably a compound having one or more radical polymerizable groups such as a group containing an ethylenically unsaturated bond, more preferably a compound having two or more radical polymerizable groups, and more preferably three The above radical polymerizable group. The upper limit of the number of radically polymerizable groups is, for example, preferably 15 or less, and more preferably 6 or less. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a styryl group, a (meth)allyl group, a (meth)acryloyl group, and the like, and a (meth)acryloyl group is preferred.

The polymerizable compound may be in any form of a monomer or a polymer, and is preferably a monomer. The molecular weight of the monomeric polymerizable compound is preferably 200 to 3000. The upper limit of the molecular weight is preferably 2500 or less, and more preferably 2000 or less. The lower limit of the molecular weight is preferably 250 or more, more preferably 300 or more.

As an example of a polymerizable compound, the description of paragraph number 0033 to paragraph number 0034 of JP 2013-253224 A can be referred to, and this content is incorporated into this specification. The compound is preferably ethyleneoxy-modified pentaerythritol tetraacrylate (the commercial product is NK Ester (NK Ester) ATM-35E; manufactured by Shinnakamura Chemical Industry Co., Ltd.), and dipentaerythritol triacrylate (commercial product is KAYARAD D-330; manufactured by Nippon Kayaku Pharmaceutical Co., Ltd.), dipentaerythritol tetraacrylate (commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Pharmaceutical Co., Ltd.), Dipentaerythritol penta(meth)acrylate (commercially available product is Kayarad (KAYARAD) D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available product is Kayarad) KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.; A-DPH-12E, manufactured by Shinnakamura Chemical Industry Co., Ltd., and these (meth)acrylic acid residues, A compound with a structure that is bonded to propylene glycol residues. In addition, these oligomer types can also be used. In addition, the description of the polymerizable compound of paragraph number 0034 to paragraph number 0038 of JP 2013-253224 A can be referred to, and the content can be incorporated into this specification. In addition, the polymerizable monomers described in paragraph No. 0477 (corresponding US Patent Application Publication No. 2012/0235099 Specification [0585]) of Japanese Patent Laid-Open No. 2012-208494 can be cited, and these contents are combined Into this manual.

In addition, diglycerol ethylene oxide (EO) modified (meth)acrylate (a commercially available product is M-460; manufactured by Toagosei Co., Ltd.) is preferred. Pentaerythritol tetraacrylate (manufactured by Shinnakamura Chemical Industry Co., Ltd., A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) are also preferred . These oligomer types can also be used. For example, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned.

As a polymerizable compound, you may have acidic groups, such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, For example, the ethylenically unsaturated compound which has an acidic group can be mentioned suitably. The polymerizable compound having an acid group can be obtained by a method such as esterifying a part of the hydroxyl group (meth)acrylate of the polyfunctional alcohol, and subjecting an acid anhydride to the remaining hydroxyl group to undergo an addition reaction to form a carboxyl group. In addition, a non-aromatic carboxylic anhydride or the like may be reacted with the hydroxyl group to introduce an acid group. Specific examples of non-aromatic carboxylic acid anhydrides include: tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylated hexahydrophthalic anhydride , Succinic anhydride, maleic anhydride.

The polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a non-aromatic carboxylic acid anhydride and an unreacted hydroxyl group of the aliphatic polyhydroxy compound are reacted to add an acid group The polymerizable compound of is more preferably a compound in which the aliphatic polyhydroxy compound in the ester is at least one of pentaerythritol and dipentaerythritol. As a commercially available product, Aronix M-510, M-520 (manufactured by Toagosei Co., Ltd.), CBX-0, CBX-1 (manufactured by Shinnakamura Chemical Industry Co., Ltd.), etc. can be cited. The acid value of the polymerizable compound having an acid group is preferably 0.1 mgKOH/g to 40 mgKOH/g. The lower limit is preferably 5 mgKOH/g or more. superior The limit is preferably 30 mgKOH/g or less.

The polymerizable compound having an acid group is preferably a compound represented by the following general formula (1).

General formula (1)(A) _n1 -L-(Ac) _n2

(In the general formula (1), A represents a hydroxyl group, L is a (n1+n2) valence group containing at least carbon atoms and hydrogen atoms, and Ac represents a (meth)acryloxy group. n1 represents an integer of 1 or more, n2 Represents an integer greater than 1)

The acid group represented by A includes a carboxyl group, a sulfo group, a phosphoric acid group, etc., and a carboxyl group is preferred.

L represents a (n1+n2) valence group containing at least a carbon atom and a hydrogen atom. For example: -CH ₂ -, -O-, -S-, -C(=O)-, -COO-, -NR-, -CONR-, -OCO-, -SO-, -SO ₂ -and A group formed by connecting two or more of these. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. L is preferably a group containing at least -CH _{2 -.} The number of carbon atoms constituting L is preferably 3-100, more preferably 6-50.

n1 is preferably 1 or 2, more preferably 1. n2 is preferably 1~6, more preferably 2~5.

The polymerizable compound having an acid group is preferably a compound represented by the following general formula (11) or (12).

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In the general formula (11), R ¹ , T ^1, and X ¹ each independently represent any of the groups shown below ^{as R 1} , T ¹ , or X ^1. n represents an integer from 0 to 14.

In the general formula (12), Z ¹ and G ¹ each independently represent any of the groups shown below ^{as Z 1} or G ^1. Yl same meaning as W ¹ of formula (11) wherein R ¹ or X ¹ represented by the presence of six or more ¹ and W 3 represents the same group as the group exemplified in R ^1, represents one or more The groups listed in X ¹ are the same groups. p represents an integer from 0 to 14.

Among the compounds represented by general formula (11) or general formula (12), it is more preferable to use at least one of a pentaerythritol derivative and a dipentaerythritol derivative.

Regarding the polymerizable compound, a compound having a caprolactone structure is also a preferable aspect. The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. Polyols such as methyl propane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylol melamine, etc. and (meth)acrylic acid and ε-hexane Ε-caprolactone obtained by esterification of lactone is modified into a multifunctional (meth)acrylate. As a compound having a caprolactone structure, refer to the paragraphs in Japanese Patent Laid-Open No. 2013-253224 The description of No. 0042~Paragraph No. 0045 is incorporated into this manual. Examples of compounds having a caprolactone structure include: DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series; SR-494, which is a tetrafunctional acrylate having four ethoxylated chains, and TPA-330, which is a trifunctional acrylate having three isobutoxy chains, manufactured by Sartomer Corporation.

Regarding polymerizable compounds, as described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765 Urethane acrylates, or Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, Japanese Patent Publication No. 62-39418 The described urethane compounds having an ethylene oxide-based skeleton are also preferable. In addition, the structures described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. 1-105238 that have an amino group structure or a thioether structure in the molecule can be used. Of addition polymerizable compounds.

Commercial products include: urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp (stock)), UA-7200 (manufactured by Shinnakamura Chemical Industry Co., Ltd.) ), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, Light Acrylate DCP-A ( Kyoeisha Chemical Co., Ltd.), etc.

In addition, the polymerizable compound can preferably use Aronix M-215, M-305, M-313, M-315 (manufactured by Toagosei Co., Ltd.), SR-368 (Sartomer) Company manufacture), A-9300 (manufactured by Shinnakamura Chemical Industry Co., Ltd.) and other isocyanuric acid ethylene oxide (EO) modified monomers.

In the composition of the present invention, the content of the polymerizable compound in the total solid content of the composition is preferably 10% by mass to 35% by mass. The lower limit is preferably 12% by mass or more, more preferably 14% by mass or more. The upper limit is preferably 33% by mass or less, more preferably 30% by mass or less.

<<Photo-radical polymerization initiator>>

The composition of the present invention contains a radical photopolymerization initiator (hereinafter, also referred to as a photopolymerization initiator). The photopolymerization initiator is not particularly limited, and can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have sensitivity to light from an ultraviolet region to a visible region. The photopolymerization initiator is preferably a photoradical polymerization initiator. In addition, the photopolymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm (more preferably, 330 nm to 500 nm).

As the photopolymerization initiator, for example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as phosphine oxide, hexaarylbiimidazole, oxime Oxime compounds such as derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, etc. Examples of halogenated hydrocarbon compounds having a triazine skeleton include: Wakabayashi et al., "Bulletin of the Chemical Society of Japan (Bull. Chem. Soc. Japan)", 42, The compound described in 2924 (1969), the compound described in British Patent No. 1388492, the compound described in Japanese Patent Laid-Open No. 53-133428, the compound described in German Patent No. 3337024, FC Schaefer (FC Schaefer "Journal of Organic Chemistry (J.Org.Chem.)", 29, 1527 (1964), the compound described in Japanese Patent Laid-Open No. 62-58241, Japanese Patent Laid-Open No. 5-281728 The compound described in Japanese Patent Laid-Open No. 5-34920, the compound described in the specification of U.S. Patent No. 4,212,976, and the like.

In addition, from the viewpoint of exposure sensitivity, it is preferably selected from the group consisting of trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, phosphine compounds, Phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron compound Compounds and their salts, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds. In addition, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (commercially available product is B-CIM, guarantee Tsuchiya Chemical Industry Co., Ltd.), etc.

As an α-amino ketone compound, the compound represented by following formula (AK-1) is mentioned.

[化42]

In the formula, Ar represents a phenyl group substituted ^{with -SR 13} or -N(R ^7E )(R ^{8E ), and R 13} represents a hydrogen atom or an alkyl group.

R ^1D and R ^2D each independently represent an alkyl group having 1 to 8 carbon atoms. R ^1D and R ^21D may be bonded to each other to form an alkylene group with 2-9 carbon atoms.

The alkyl group represented by R ^1D and R ^2D may be linear, branched, and cyclic, and is preferably linear or branched.

The alkyl group represented by R ^1D and R ^2D may be unsubstituted or may have a substituent. Examples of substituents include aryl groups, heterocyclic groups, nitro groups, cyano groups, halogen atoms, -OR ^Y1 , -SR ^Y1 , -COR ^Y1 , -COOR ^Y1 , -OCOR ^Y1 , -NR ^Y1 R ^Y2 ,- NHCOR ^Y1 , -CONR ^Y1 R ^Y2 , -NHCONR ^Y1 R ^Y2 , -NHCOOR ^Y1 , -SO ₂ R ^Y1 , -SO ₂ OR ^Y1 , -NHSO ₂ R ^Y1 and so on. R ^Y1 and R ^Y2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Among these, the substituent of the alkyl group represented by ^{R 1D} and R ^{2D is preferably an aryl group.} It is particularly ^{preferable that any one of R 1D} and R ^2D is an unsubstituted alkyl group, and the other is an alkyl group substituted with an aryl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The number of carbon atoms in the alkyl group represented by ^{R Y1} and R ^{Y2 is preferably 1-20.} The alkyl group may be any of linear, branched, and cyclic, and is preferably linear or branched.

The number of carbon atoms in the aryl group as a substituent and the aryl group ^{represented by R Y1} and R ^Y2 is preferably 6-20, more preferably 6-15, and still more preferably 6-10. The aryl group may be a single ring or a condensed ring.

The heterocyclic group represented by R ^Y1 and R ^Y2 is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a monocyclic ring or a condensed ring. The number of carbon atoms constituting the heterocyclic group is preferably 3-30, more preferably 3-18, and still more preferably 3-12. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.

R ^3D and R ^4D each independently represent a hydrogen atom, an alkyl group with 1 to 12 carbons, an alkyl group with 2 to 4 carbons substituted by an alkoxy group with 1 to 4 carbons, or an alkene with 3 to 5 carbons. base. R ^3D and R ^4D may be bonded to each other to form a ring.

R ^7E and R ^8E each independently represent a hydrogen atom, an alkyl group with 1 to 12 carbons, an alkyl group with 2 to 4 carbons substituted by an alkoxy group with 1 to 4 carbons, or an alkene with 3 to 5 carbons. base. R ^7E and R ^8E may be bonded to each other to form a ring.

Examples of the compound represented by the formula (AK-1) include: 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1-[4-(hexyl )Phenyl)-2-morpholinylpropane-1-one, 2-ethyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-benzyl -2-Dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl] -1-[4-(4-morpholinyl)phenyl]-1-butanone and the like.

Commercial products of α-amino ketone compounds include: IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names, all manufactured by BASF) )Wait.

The photopolymerization initiator can also preferably use α-hydroxy ketone compounds and acyl groups Phosphine compounds. As α-hydroxy ketone compounds, IRGACURE 184, DAROCUR 1173, IRGACURE 500, IRGACURE 2959, IRGACURE 127 (commodity products) can be used as α-hydroxy ketone compounds. Names, all manufactured by BASF (BASF). As the phosphine compound, commercially available IRGACURE 819 or IRGACURE TPO (trade names, both manufactured by BASF) can be used.

The photopolymerization initiator is also preferably an oxime compound. As specific examples of the oxime compound, the compound described in Japanese Patent Laid-Open No. 2001-233842, the compound described in Japanese Patent Laid-Open No. 2000-80068, and the compound described in Japanese Patent Laid-Open No. 2006-342166 can be used. , The compound described in Japanese Patent Laid-Open No. 2016-21012.

In the present invention, as an oxime compound that can be preferably used, for example, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one , 3-Propyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1 -Ketone, 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxy Carbonyloxyimino-1-phenylpropan-1-one and the like. In addition, you can also list "The Journal of the British Chemical Society-Pulkin II (JCSPerkin II)" ((1979) pages 1653-1660), "The Journal of the British Chemical Society-Pulkin II (JCSPerkin II)" '' ((1979) pages 156-162), "Journal of Photopolymer Science and Technology" ((1995) pages 202-232), Japanese Patent Laid-Open No. 2000-66385 The compound described in the bulletin, Japanese Patent Laid-Open No. 2000-80068 The compounds described in the gazettes, Japanese Patent Application Publication No. 2004-534797, and Japanese Patent Application Publication No. 2006-342166, etc. Among the commercially available products, IRGACURE OXE01 (manufactured by BASF Corporation) and IRGACURE OXE02 (manufactured by BASF Corporation) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Adeka Arkls NCI-930 (manufactured by ADEKA (stock)) can be used.

In addition, as an oxime compound other than the above description, the compound described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N position of the carbazole ring, and a heterosubstituent group introduced into the benzophenone site can also be used. The compound described in U.S. Patent No. 7626957, the compound described in Japanese Patent Laid-Open No. 2010-15025 and U.S. Patent Publication No. 2009-292039, and International Publication No. 2009/131189, in which a nitro group is introduced into the pigment site The ketoxime compound described in U.S. Patent No. 7556910, which contains a triazine skeleton and an oxime skeleton in the same molecule, has a maximum absorption wavelength at 405 nm and has good sensitivity to g-ray light sources in Japanese Patent Laid-Open The compound described in 2009-221114 A, the compound described in paragraph number 0076 to paragraph number 0079 of JP 2014-137466 A, and the like.

Preferably, for example, Paragraph No. 0274 to Paragraph No. 0275 of JP 2013-29760 A can be referred to, and the content can be incorporated into this specification.

Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The oxime compound can be an oxime compound in which the N-O bond of the oxime is an (E) body, or the N-O of the oxime The oxime compound whose bond is a (Z) body, or it may be a mixture of (E) body and (Z) body.

In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

In formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metal atomic group.

Examples of the monovalent non-metal atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, an arylthiocarbonyl group, and the like. In addition, these groups may have one or more substituents. In addition, the substituent may be further substituted with other substituents.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, an aryl group, and the like.

In the formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have more than one substituent. As the substituent, the above-mentioned substituents can be exemplified.

In the formula (OX-1), the divalent organic group represented by A is preferably an alkylene group, cycloalkylene group, or alkynylene group having 1 to 12 carbon atoms. These groups may have more than one substituent. As the substituent, the above-mentioned substituents can be exemplified.

In the present invention, an oxime compound having a sulphur ring can also be used as a photopolymerization initiator. As a specific example of the oxime compound which has a sulphur ring, the compound described in Unexamined-Japanese-Patent No. 2014-137466 is mentioned. Incorporate this content into this manual.

In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include the compound described in Japanese Patent Laid-Open No. 2010-262028, the compound 24 described in the Japanese Patent Publication No. 2014-500852, the compound 36 to the compound 40, and the Japanese Patent The compound (C-3) described in JP 2013-164471 A, etc. Incorporate this content into this manual.

In the present invention, an oxime compound having a nitro group can be used as a photopolymerization initiator. The oxime compound having a nitro group is also preferably used as a dimer. Specific examples of the oxime compound having a nitro group include paragraph numbers 0031 to 0047 of Japanese Patent Laid-Open No. 2013-114249, paragraph numbers 0008 to paragraph number 0012 of Japanese Patent Laid-Open No. 2014-137466, and paragraphs. No. 0070 ~ Paragraph No. 0079 The compound described in Paragraph No. 0007 of Japanese Patent No. 4223071 ~ Paragraph No. 0025 The compound described in Paragraph No. 0025, Adeka Arkls NCI-831 (ADEKA) (Stock) Manufacturing).

Specific examples of oxime compounds that can be preferably used in the present invention are shown below, but the present invention is not limited to these.

[化44]

[化45]

The oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably a compound having a maximum absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably a compound having high absorbance at 365 nm and 405 nm.

From the viewpoint of sensitivity, the molar absorption coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The molar absorption coefficient of the compound can be measured by a known method. Specifically, for example, an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) is preferred. )) and use ethyl acetate solvent and at a concentration of 0.01g/L Perform the measurement.

The photopolymerization initiator also preferably contains an oxime compound and an α-aminoketone compound. By using both together, it is easy to form a pattern with improved developability and excellent rectangularity. When the oxime compound and the α-amino ketone compound are used in combination, the α-amino ketone compound is preferably 50 parts by mass to 600 parts by mass, more preferably 150 parts by mass to 400 parts by mass relative to 100 parts by mass of the oxime compound .

Relative to the total solid content of the composition of the present invention, the content of the photopolymerization initiator is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, and still more preferably 1% by mass to 20% by mass %. Within this range, better sensitivity and pattern formability can be obtained. The composition of the present invention may include only one type of photopolymerization initiator, or may include two or more types. When two or more types are contained, it is preferable that the total amount falls within the said range.

<<Resin>>

The composition of the present invention contains a resin. The resin is formulated for the purpose of dispersing pigments and the like in the composition and the use of a binder, for example. In addition, the resin mainly used for dispersing pigments etc. is also called a dispersing agent. Among them, such use of the resin is an example, and it can also be used for purposes other than such use.

In the present invention, the resin includes a resin having an acid group. As an acid group, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, etc. are mentioned, Preferably it is a carboxyl group. A resin having an acid group can be used, for example, as an alkali-soluble resin or dispersant described later.

The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3,000 Above, more preferably 5,000 or above. In addition, in the case of an epoxy resin, the weight average molecular weight (Mw) of the epoxy resin is preferably 100 or more, more preferably 200 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 100 or more, more preferably 200 or more.

(Alkali-soluble resin)

The composition of the present invention preferably contains an alkali-soluble resin as the resin. When the composition of the present invention contains an alkali-soluble resin, developability and pattern formability are improved.

The alkali-soluble resin can be appropriately selected from resins having a group that promotes alkali solubility.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 to 100,000. In addition, the number average molecular weight (Mn) of the alkali-soluble resin is preferably 1,000 to 20,000. The acid value of the alkali-soluble resin is preferably 30 mgKOH/g to 500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more, and still more preferably 70 mgKOH/g or more. The upper limit is more preferably 400 mgKOH/g or less, further preferably 200 mgKOH/g or less, particularly preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.

As the alkali-soluble resin, from the viewpoint of heat resistance, polyhydroxy styrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic/acrylamide copolymer resins are preferred. From the viewpoint of controlling developability, acrylic resins, acrylamide resins, and acrylic/acrylamide copolymer resins are preferred.

Examples of groups that promote alkali solubility (hereinafter also referred to as acid groups) include carboxyl groups, phosphoric acid groups, sulfonic acid groups, phenolic hydroxyl groups, etc., and are preferably soluble in organic solvents. And it can be developed by weak alkaline aqueous solution, especially preferably carboxyl group. The acid group may be only one type or two or more types.

The alkali-soluble resin is preferably a polymer having a carboxyl group in the side chain, and examples thereof include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, and partially esterified maleic acid. An acid copolymer, a novolak type resin, and an acidic cellulose derivative having a carboxyl group in a side chain, and a polymer obtained by adding an acid anhydride to a polymer having a hydroxyl group. In particular, it is preferable to use a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, vinyl compounds, and the like. Examples of alkyl (meth)acrylate and aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylate. Butyl acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylic acid Benzyl ester, toluene (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc., as vinyl compounds, can be Examples: styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomers, polymethyl methacrylate macromonomers, etc. Examples of the N-substituted maleimide monomers described in Japanese Patent Laid-Open No. 10-300922 include N-phenylmaleimide, N-cyclohexylmaleimide, and the like. Furthermore, these other monomers that can be copolymerized with (meth)acrylic acid may be only one type or two or more types.

Alkali-soluble resin can preferably use benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/(meth)acrylic acid 2-hydroxyethyl copolymer , A multi-element copolymer containing benzyl (meth)acrylate/(meth)acrylic acid/other monomers. In addition, a copolymer of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate/polystyrene described in Japanese Patent Laid-Open No. 7-140654 can also be preferably used. Macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid Copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/formaldehyde Benzyl acrylate/methacrylic acid copolymer, etc. In addition, as a commercially available product, for example, FF-426 (manufactured by Fujikura Kasei Co., Ltd.) or the like can also be used.

The alkali-soluble resin also preferably contains a polymer obtained by polymerizing monomer components, the monomer components including a compound represented by the following formula (ED1) and a compound represented by the following formula (ED2) (hereinafter, These compounds are also referred to as at least one of "ether dimers").

In the formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 25 carbon atoms.

In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), reference can be made to the description in Japanese Patent Laid-Open No. 2010-168539.

In the formula (ED1), ^{the optionally substituted hydrocarbon group with 1 to 25 carbons represented by R 1} and R ² is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl, and n-propyl. Butyl, isobutyl, tertiary butyl, tertiary pentyl, stearyl, lauryl, 2-ethylhexyl and other linear or branched alkyl groups; phenyl and other aryl groups; cyclohexyl, the first Alicyclic groups such as tributylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, 2-methyl-2-adamantyl, etc.; 1-methoxyethyl , 1-ethoxyethyl and other alkyl substituted by alkoxy; benzyl and other alkyl substituted by aryl, etc. Among these, in terms of heat resistance, a substituent of a primary carbon or a secondary carbon, such as a methyl group, an ethyl group, a cyclohexyl group, and a benzyl group, which is not easily removed by acid or heat, is particularly preferred.

As a specific example of the ether dimer, for example, paragraph number 0317 of JP 2013-29760 A can be referred to, and this content is incorporated in this specification. There may be only one type of ether dimer, or two or more types.

Alkali-soluble resin may also contain the repeating unit derived from the compound represented by following formula (X).

In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms that may contain a benzene ring. n represents an integer of 1-15.

In the formula (X), the carbon number of the alkylene group of _{R 2 is preferably 2-3.} Moreover, _{the carbon number of the alkyl group of R 3} is 1-20, More preferably, it is 1-10, and _{the alkyl group of R 3} may contain a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group, a 2-phenyl(iso)propyl group, and the like.

Alkali-soluble resins can also use graft copolymers. In addition, in the present invention, the so-called graft copolymer refers to a resin having a graft chain. In addition, the term “graft chain” means from the root of the main chain of the polymer to the end of the group branched from the main chain.

The graft copolymer is preferably a resin having a graft chain in the range of 40 to 10,000 atoms other than hydrogen atoms. In addition, the number of atoms other than hydrogen atoms in each grafted chain is preferably 40 to 10,000, more preferably 50 to 2,000, and still more preferably 60 to 500.

As the main chain structure of the graft copolymer, one can cite: (meth)acrylic resin Grease, polyester resin, polyurethane resin, polyurea resin, polyamide resin, polyether resin, etc. Among them, (meth)acrylic resin is preferred. In order to improve the interaction between the grafting site and the solvent and thereby improve the dispersibility, the graft chain of the graft copolymer preferably has a graft chain of poly(meth)acrylic acid, polyester, or polyether, and more Preferably, it has a graft chain of polyester or polyether.

The graft copolymer preferably contains a repeating unit represented by any of the following formulas (1) to (4).

In formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH, and X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent hydrogen Atom, monovalent group, Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent group, R ³ represents an alkane R ⁴ represents a hydrogen atom or a monovalent group, n, m, p, and q each independently represent an integer of 1 to 500, and j and k each independently represent an integer of 2 to 8. In formula (3), when p is 2 to 500, multiple R ³ may be the same as or different from each other. In formula (4), when q is 2 to 500, X ⁵ and R ⁴ that are present in plural may be the same or different from each other.

W ¹ , W ² , W ³ and W ^{4 are} preferably oxygen atoms.

X ¹ , X ² , X ³ , X ⁴ and X ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbons, more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.

Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group. As a divalent linking group, the group containing -CO-, -O-, -NH-, an alkylene group, an arylene group, and a combination of these can be mentioned.

The structure of the monovalent group represented by Z ¹ , Z ² , Z ³ and Z ^{4 is not particularly limited.} For example, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkyl sulfide group, an aryl sulfide group, a heteroaryl sulfide group, an amino group, etc. are mentioned.

In formula (1) to formula (4), n, m, p, and q are each independently an integer of 1 to 500. In addition, in formula (1) and formula (2), j and k each independently represent an integer of 2-8. From the viewpoint of dispersion stability and developability, j and k in formula (1) and formula (2) are preferably an integer of 4 to 6, and most preferably 5.

In the formula (3), R ³ represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, multiple R ³ may be the same as or different from each other.

In formula (4), R ⁴ represents a hydrogen atom or a monovalent group. R ^{4 is} preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. In formula (4), when q is 2 to 500, X ⁵ and R ⁴ that exist in plural may be the same as or different from each other.

For the details of the formula, refer to the descriptions of paragraph numbers 0025 to 0069 in Japanese Patent Laid-Open No. 2012-255128, and The content is incorporated into this specification.

As a specific example of alkali-soluble resin, the following can be mentioned.

Alkali-soluble resins can refer to paragraphs 0558 to 0571 of Japanese Patent Laid-Open No. 2012-208494 (corresponding U.S. Patent Application Publication No. 2012/0235099 [0685] to [0700]). These contents are incorporated into this manual. In addition, the copolymer (B) described in paragraph number 0029 to paragraph number 0063 of JP 2012-32767 A, the alkali-soluble resin used in the examples, and Japanese Patent Laid-Open No. 2012-208474 can also be used. The adhesive resin described in paragraph number 0088 to paragraph number 0098 and the adhesive resin used in the examples, and the adhesive resin described in paragraph number 0022 to paragraph number 0032 of Japanese Patent Laid-Open No. 2012-137531 and implementation The adhesive resin used in the examples, the adhesive resin described in paragraph numbers 0132 to 0143 of Japanese Patent Laid-Open No. 2013-024934, and the adhesive resin used in the examples, Japanese Patent Laid-Open No. 2011-242752 The adhesive resin described in paragraph number 0092 to paragraph number 0098 and the adhesive resin used in the examples, and the adhesive resin described in paragraph number 0030 to paragraph number 0072 of Japanese Patent Laid-Open No. 2012-032770 . These contents are incorporated into this manual.

Alkali-soluble resins having polymerizable groups may also be used for alkali-soluble resins. As a polymerizable group, a (meth)allyl group, a (meth)acryloyl group, etc. are mentioned. Among alkali-soluble resins having polymerizable groups, alkali-soluble resins containing polymerizable groups in the side chain and the like are useful. Examples of alkali-soluble resins containing polymerizable groups include: Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (polyurethane acrylic oligomer containing COOH) Polymer, Diamond Shamrock Co., Ltd. (manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264, KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Placcel CF200 series (all manufactured by Daicel (stock)), Ebecryl 3800 (Dacell UCB ( Daicel UCB (Stock), Acrycure RD-F8 (Nippon Shokubai Co., Ltd.), etc.

(Dispersant)

The composition of the present invention may contain a dispersant in the form of a resin. In the case of using a pigment, it is particularly preferable to include a dispersant. Examples of the dispersant include acidic dispersants (acidic resins) and basic dispersants (alkaline resins). The dispersant preferably contains at least an acidic dispersant, and more preferably only an acidic dispersant. When the dispersant contains at least an acidic dispersant, the dispersibility of the pigment is improved, and excellent developability can be obtained. Therefore, photolithography can be used for better pattern formation. In addition, the so-called dispersant is only an acidic dispersant. For example, the content of the acidic dispersant in the total mass of the dispersant is preferably 99% by mass or more, and may be 99.9% by mass or more.

Here, the so-called acidic dispersant (acidic resin) means that the amount of acid groups is large The amount of the resin in the basic group. When the total amount of the amount of acid groups and the amount of basic groups is set to 100 mol%, the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups occupies 70 mol% or more, and more preferably is substantial. The above resin contains only acid groups. The acid group possessed by the acidic dispersant (acid resin) is preferably a carboxyl group.

In addition, the so-called basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acid groups. When the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, the basic dispersant (alkaline resin) is preferably a resin in which the amount of basic groups accounts for 50 mol% or more. The basic group possessed by the basic dispersant is preferably an amino group.

The acid value of the acidic dispersant (acid resin) is preferably 40mgKOH/g~105mgKOH/g, more preferably 50mgKOH/g~105mgKOH/g, and still more preferably 60mgKOH/g~105mgKOH/g.

The resin used as a dispersant preferably contains a repeating unit having an acid group. Since the resin contains repeating units with acid groups, when the pattern is formed by photolithography, the residue generated on the pixel substrate can be further reduced.

In addition, the resin used as a dispersant is also preferably a graft copolymer. The graft copolymer has affinity with the solvent due to the graft chain, and therefore the dispersibility of the pigment and the dispersion stability over time are excellent. In addition, the composition has affinity with polymerizable compounds, alkali-soluble resins, etc. due to the presence of graft chains, and therefore it is difficult to generate residues during alkali development. Examples of the graft copolymer include resins containing repeating units represented by any one of formula (1) to formula (4) described in the alkali-soluble resin. For example, the following resins can be mentioned. In addition, the following resins can also be used as alkali-soluble resins.

[化51]

The dispersant can also be used in oligoimine resins in which at least one of the main chain and the side chain contains a nitrogen atom. The oligoimine-based resin is preferably a resin having a repeating unit and a side chain containing a group X, and at least one of the main chain and the side chain has a basic nitrogen atom, and the group X contains a functional group having a pKa of 14 or less. The partial structure of the group, the side chain includes a side chain Y with 40 to 10,000 atoms. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.

The oligoimine-based resin may include at least any one of the repeating unit represented by formula (I-1), the repeating unit represented by formula (I-2), and the repeating unit represented by formula (I-2a), for example. The resin and so on.

R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or an alkyl group (preferably having 1 to 6 carbon atoms). a represents an integer of 1 to 5 independently of each other. * Indicates the connection between the repeating units.

R ⁸ and R ⁹ have the same meaning as R ^1.

L is a single bond, alkylene (preferably carbon number 1 to 6), alkenylene (preferably carbon number 2 to 6), arylene group (preferably carbon number 6 to 24), heteroarylene Group (preferably carbon number 1 to 6), imino group (preferably carbon number 0 to 6), ether group, thioether group, carbonyl group, or linking group in a combination of these. Among them, a single bond or -CR ⁵ R ⁶ -NR ^7- (imino group becomes X or Y) is preferred. Here, R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, and an alkyl group (preferably carbon number 1 to 6). R ⁷ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

La is ^a structural part that forms a ring structure together with CR ⁸ CR ⁹ and N, and is preferably a structural part that forms a non-aromatic heterocyclic ring with 3 to 7 carbons together with the carbon atom of ^{CR 8} CR ^9. It is more preferable to form a 5-member to 7-membered non-aromatic heterocyclic structure site together with the carbon atom of ^{CR 8} CR ^{9 and N (nitrogen atom), and it is more preferable to form a 5-membered non-aromatic heterocyclic structure site} , It is particularly preferred to form the structural part of pyrrolidine. This structural part may further have substituents, such as an alkyl group.

X represents a group containing a partial structure having a functional group having pKa 14 or less.

Y represents a side chain with 40 to 10,000 atoms.

The resin (oligoimine-based resin) may further contain one or more selected from repeating units represented by formula (I-3), formula (I-4), and formula (I-5) as a copolymerization component. Since the resin contains such a repeating unit, the dispersibility of the pigment can be further improved.

[化53]

^{R 1, R 2, R 8} , R 9,, the same provisions of the formula (I-2a) L, L a, a * and the meanings of formula (I-1), formula (I-2).

Ya represents a side chain with 40 to 10,000 atoms having an anionic group. The repeating unit represented by the formula (I-3) can be made by adding an oligomer or polymer having a group that reacts with an amine to form a salt to a resin having a primary or secondary amine group in the main chain. It is formed by reaction.

Regarding the oligoimine-based resin, reference can be made to the description of paragraph number 0102 to paragraph number 0166 of JP 2012-255128 A, and the content is incorporated into this specification. As a specific example of an oligoimine resin, the following can be mentioned, for example. In addition, the resins described in paragraph numbers 0168 to 0174 of JP 2012-255128 A can be used.

The dispersant may also use a resin containing a repeating unit represented by the following formula (P1).

In the formula (P1), R ¹ represents hydrogen or methyl, R ² represents an alkylene group, and Z represents a nitrogen-containing heterocyclic structure.

The ^{alkylene group represented by R 2} is not particularly limited. For example, preferred examples include: methylene, ethylene, trimethylene, tetramethylene, hexamethylene, 2-hydroxypropylene, ethylene Methoxy, ethyleneoxy, methyleneoxycarbonyl, methylenethio, etc., more preferably methylene, methyleneoxy, methyleneoxycarbonyl, methylenethio.

The nitrogen-containing heterocyclic structure represented by Z includes, for example, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a quinoline ring, an acridine ring, and a phenanthrene ring. Thiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benzotriazole structure, benzothiazole structure, cyclic amide structure, cyclic urea structure and cyclic imide Structurer. Among these, the nitrogen-containing heterocyclic structure represented by Z is preferably a structure represented by the following formula (P2) or formula (P3).

[化56]

In the formula, X is a single bond, selected from alkylene (for example, methylene, ethylene, propylene, trimethylene, tetramethylene, etc.), -O-, -S-, -NR- And any one of the group consisting of -C(=O)-. In addition, here, R represents a hydrogen atom or an alkyl group. Among these, X is preferably a single bond, methylene, -O-, -C(=O)-, and particularly preferably -C(=O)-.

In the formula, ring A, ring B, and ring C each independently represent an aromatic ring. Examples of the aromatic ring include benzene ring, naphthalene ring, indene ring, azulene ring, pyridine ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, Acridine ring, phenanthrazine ring, phenanthrazine ring, acridone ring, anthraquinone ring, etc., among which benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenanthrazine ring, acridine ring, Phthiazine ring, acridone ring, anthraquinone ring, particularly preferably benzene ring, naphthalene ring and pyridine ring.

As a specific example of the repeating unit represented by formula (P1), the following can be mentioned, for example. In addition, the description of paragraph number 0023 of JP 2008-009426 A can be referred to, and the content can be incorporated into this specification.

[化57]

As a specific example of the resin containing the repeating unit represented by Formula (P1) and another repeating unit, the following can be mentioned.

Dispersants can also be obtained as commercially available products. Specific examples of this include: "DA-7301" manufactured by Kusumoto Chemical Co., Ltd.; "Disperbyk" manufactured by BYK Chemie. )-101 (polyamide phosphate), 107 (carboxylate), 110 (acid group-containing copolymer), 111 (phosphate-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer)"; "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)" manufactured by BYK Chemie; EFKA (EFKA) ) EFKA (EFKA) 4047, 4050-4165 (polyurethane series), EFKA (EFKA) manufactured by the company 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine) Derivatives), 6750 (Azo pigment derivatives)"; "Ajisper PB821, PB822, PB880, PB881" manufactured by Ajinomoto Fine-Techno (Stock); Kyoeisha "Flowlen TG-710 (urethane oligomer)", "Polyflow No.50E, No.300 (acrylic copolymer)" manufactured by Chemical Co., Ltd. ; "Disparlon (Disparlon) KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA- 705, DA-725"; "Demol RN, N (formalin naphthalenesulfonate condensation polymer), MS, C, SN-B (aromatic formalin sulfonate condensation polymer) manufactured by Kao Co., Ltd. "; "Homogenol L-18 (polymer polycarboxylic acid)" manufactured by Kao (Stock); "Emulgen (Emulgen) 920, 930, 935, 985 () manufactured by Kao (Stock) Polyoxyethylene nonyl phenyl ether"; "Acetamin 86 (stearyl amine acetate)" manufactured by Kao; manufactured by Lubrizol (Stock) in Japan Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (functional part at the end) Polymer), 24000, 28000, 32000, 38500 (grafted polymer)"; "Nikkol T106 (polyoxyethylene sorbitan) manufactured by Nikko Chemicals (stock) Monooleate), MYS-IEX (polyoxyethylene monostearate)"; "Hinoact T-8000E" manufactured by Kawaken Fine Chemicals (stock); Shin-Etsu Chemical Industry Co., Ltd. "Organosiloxane polymer KP341" manufactured by Morishita Industry Co., Ltd. "EFKA-46, EFKA-47, EFKA-47EA, EFKA (EFKA) polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450"; manufactured by San Nopco (Stock) "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100" ; "Adeka Pluronic (Adeka Pluronic) L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101) manufactured by ADEKA (stock) , P103, F108, L121, P-123"; and "Ionet S-20" manufactured by Sanyo Chemical Co., Ltd. etc.

The mass ratio of the radical polymerizable compound to the resin of the composition of the present invention is radical polymerizable compound/resin=0.3 to 0.7. The lower limit of the mass ratio is preferably 0.35 or more, more preferably 0.4 or more. The upper limit of the mass ratio is preferably 0.65 or less, more preferably 0.6 or less. If the mass ratio is in the above range, a pattern excellent in rectangularity can be formed.

The mass ratio of the radical polymerizable compound and the resin having an acid group of the composition of the present invention is preferably that the radical polymerizable compound/resin having an acid group=0.3 to 0.7. The lower limit of the mass ratio is preferably 0.35 or more, more preferably 0.4 or more. The upper limit of the mass ratio is preferably 0.65 or less, more preferably 0.6 or less. If the mass ratio is in the above range, a pattern excellent in rectangularity can be formed.

Radical polymerizable compound and alkali-soluble resin of the composition of the present invention The better quality of the fat is radical polymerizable compound/alkali-soluble resin=0.3~0.7. The lower limit of the mass ratio is preferably 0.35 or more, more preferably 0.4 or more. The upper limit of the mass ratio is preferably 0.65 or less, more preferably 0.6 or less. If the mass ratio is in the above range, a pattern excellent in rectangularity can be formed.

In the composition of the present invention, the content of the resin is preferably 14% by mass to 70% by mass relative to the total solid content of the composition of the present invention. The lower limit is preferably 17% by mass or more, more preferably 20% by mass or more. The upper limit is preferably 56% by mass or less, and more preferably 42% by mass or less.

In the composition of the present invention, the content of the resin having an acid group is preferably 14% by mass to 70% by mass relative to the total solid content of the composition of the present invention. The lower limit is preferably 17% by mass or more, more preferably 20% by mass or more. The upper limit is preferably 56% by mass or less, and more preferably 42% by mass or less.

In the composition of the present invention, the content of the alkali-soluble resin is preferably 14% by mass to 70% by mass relative to the total solid content of the composition of the present invention. The lower limit is preferably 17% by mass or more, more preferably 20% by mass or more. The upper limit is preferably 56% by mass or less, and more preferably 42% by mass or less.

<<Chain transfer agent>>

The composition of the present invention preferably contains a chain transfer agent. According to this aspect, the hardening of the film surface (pattern surface) can be promoted by exposure at the time of pattern formation. Therefore, it is possible to suppress the reduction of the film thickness during exposure, etc., and it is easy to form a pattern with more excellent rectangularity.

Examples of the chain transfer agent include N,N-dialkylaminobenzoic acid alkyl esters, thiol compounds, and the like, and thiol compounds are preferred. The thiol compound is preferably intramolecular A compound having two or more (preferably 2 to 8, more preferably 3 to 6) thiol groups. Specific examples of thiol compounds include: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, N-phenylmercaptobenzimidazole, 1,3,5-tris( 3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and other thiol compounds with heterocycles, pentaerythritol tetra(3-mercaptobutane) Aliphatic thiol compounds such as acid ester), 1,4-bis(3-mercaptobutanoyloxy)butane, etc. In addition, the following compounds are also preferably used. In addition, as commercial products of the chain transfer agent, PEMP (manufactured by Nagase Sangyo Co., Ltd., thiol compound), Sanceler M (manufactured by Sanshin Chemical Co., Ltd., thiol compound) , Karenz (Karenz) MT BD1 (manufactured by Showa Denko Co., Ltd., mercaptan compound) and so on.

Relative to the total solid content of the composition, the content of the chain transfer agent is preferably 0.2% by mass to 5.0% by mass, more preferably 0.4% by mass to 3.0% by mass.

The content of the chain transfer agent is preferably 1 part by mass to 40 parts by mass, and more preferably 2 parts by mass to 20 parts by mass relative to 100 parts by mass of the radically polymerizable compound.

<<Compounds with epoxy groups>>

The composition of the present invention may also contain a compound having an epoxy group. Examples of the compound having an epoxy group include monofunctional or polyfunctional glycidyl ether compounds, or polyfunctional aliphatic glycidyl ether compounds. In addition, compounds having an alicyclic epoxy group may also be used.

Examples of the compound having an epoxy group include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred. The epoxy group preferably has 1 to 100 in one molecule. The upper limit of epoxy groups may be 10 or less, for example, and may be 5 or less. The lower limit of epoxy groups is preferably 2 or more.

The epoxy equivalent of the epoxy-containing compound (= the molecular weight of the epoxy-containing compound/the number of epoxy groups) is preferably 500 g/equivalent or less, more preferably 100 g/equivalent to 400 g/equivalent, and more preferably 100g/equivalent to 300g/equivalent.

The compound having an epoxy group may be a low-molecular compound (for example, the molecular weight is less than 2000, and the molecular weight is less than 1000), or a macromolecule (for example, the molecular weight is 1000 or more, in the case of a polymer, The weight average molecular weight is 1000 or more). The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10000 or less, more preferably 5000 or less, and The best value is 3000 or less.

The compound having an epoxy group can also use paragraph numbers 0034 to 0036 of Japanese Patent Laid-Open No. 2013-011869, paragraph numbers 0147 to 0156 of Japanese Patent Laid-Open No. 2014-043556, and Japanese Patent Laid-Open No. 2014 -089408, Paragraph No. 0085 to Paragraph No. 0092 of the compound. These contents are incorporated into this manual. As commercially available products, for example, bisphenol A epoxy resins are jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (the above are manufactured by Mitsubishi Chemical Corporation), Abbecron ( EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (the above are manufactured by DIC (stock)), etc. The bisphenol F epoxy resin is jER806, jER807, jER4004, jER4005, jER4007, jER4010 (manufactured by Mitsubishi Chemical Corporation), EPICLON 830, EPICLON 835 (manufactured by DIC Corporation) , LCE-21, RE-602S (manufactured by Nippon Kayaku Co., Ltd.), etc., phenol novolac type epoxy resin is jER152, jER154, jER157S70, jER157S65 (manufactured by Mitsubishi Chemical Co., Ltd.), Abikron (EPICLON) N-740, Epiclon (EPICLON) N-770, Epiclon (EPICLON) N-775 (the above are manufactured by DIC (Stock)), etc. The cresol novolac type epoxy resin is EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON EPICLON N-695 (the above is manufactured by DIC), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), etc. The aliphatic epoxy resin is ADEKA RESIN EP -4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (the above are manufactured by ADEKA (stock)), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (The above is the competition Daicel (Stock), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (the above are manufactured by Nagase ChemteX (Stock) )Wait. In addition to this, you can also list: ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN RESIN) EP-4011S (the above are manufactured by ADEKA (stock)), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (the above are ADEKA ( ADEKA) (manufactured by Mitsubishi Chemical Co., Ltd.), jER1031S (manufactured by Mitsubishi Chemical Co., Ltd.), OXT-221 (manufactured by Toagosei Co., Ltd.), etc.

As the compound having an epoxy group, the compound described in paragraph number 0045 of JP 2009-265518 A, etc. can also be used.

In the total solid content of the composition, the content of the compound having an epoxy group is preferably 0.5% by mass to 20% by mass. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less.

<<Solvent>>

The composition of the present invention may contain a solvent. As the solvent, organic solvents can be cited. The solvent is basically not particularly limited as long as it satisfies the solubility of each component or the coatability of the composition, and it is preferably selected in consideration of the coatability and safety of the composition.

As an example of an organic solvent, the following can be mentioned, for example. Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate Ester, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkoxy acetate (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methoxy Methyl ethoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkoxypropionic acid alkyl esters (for example, Methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl ester, 3-ethoxy ethyl propionate, etc.)), 2-alkoxy propionic acid alkyl esters (e.g. 2-alkoxy methyl propionate, 2-alkoxy ethyl propionate, Propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropionic acid Methyl ester, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, 2-methyl Methyl oxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, Ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, two Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether Ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. As ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. are mentioned, for example. Examples of aromatic hydrocarbons include toluene and xylene. Among them, the aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as solvents are preferably reduced due to environmental reasons (for example, it can be set to 50 relative to the total amount of organic solvents). Mass ppm or less, may also be 10 mass ppm or less, or may be 1 mass ppm or less).

One kind of organic solvent may be used alone, or two or more kinds may be used in combination. When two or more organic solvents are used in combination, they are preferably selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, and lactic acid. Ethyl ester, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate A mixed solution of two or more of esters, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.

In the present invention, it is preferable to use a solvent with a small metal content, and the metal content of the solvent is preferably 10 mass ppb or less, for example. It is also possible to use ppt-level solvents as needed. Such high-purity solvents are, for example, provided by Toyo Gosei Kogyo Co., Ltd. (Chemical Industry Daily, November 13, 2015).

As a method of removing impurities such as metals from the solvent, for example, distillation (molecular distillation, thin film distillation, etc.) or filtration using a filter can be cited. The pore size of the filter in filtration using a filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable.

The solvent may include isomers (compounds with the same atomic type and number and different structures). In addition, the isomer may include only one type or multiple types.

In the present invention, the peroxide content of the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.

The content of the solvent relative to the total amount of the composition is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and still more preferably 25% by mass to 75% by mass.

<<Silane Coupling Agent>>

The composition of the present invention may further contain a silane coupling agent. Furthermore, in the present invention, the silane coupling agent is a component different from the above-mentioned polymerizable compound. In the present invention, the silane coupling agent refers to a silane compound having a hydrolyzable group and other functional groups. In addition, the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. As a hydrolyzable group, a halogen atom, an alkoxy group, an acyloxy group, etc. are mentioned, for example, Preferably it is an alkoxy group. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. In addition, the functional group other than the hydrolyzable group is preferably a group that forms an interaction or bond with the resin to show affinity. For example, a (meth)acryloyl group, a phenyl group, a mercapto group, an epoxy group, and an oxetanyl group are mentioned, and a (meth)acryloyl group and an epoxy group are preferable. That is, the silane coupling agent is preferably a compound having at least one of an alkoxysilyl group, a (meth)acryloyl group, and an epoxy group. The silane coupling agent includes the compounds described in paragraph number 0018 to paragraph number 0036 of JP 2009-288703, and the compounds described in paragraph number 0056 to paragraph number 0006 of JP 2009-242604. The content is incorporated into this specification.

The content of the silane coupling agent is preferably 0.01% by mass to 15.0% by mass, and more preferably 0.05% by mass to 10.0% by mass relative to the total solid content of the composition. The silane coupling agent may be only one type or two or more types. In the case of two or more types, it is preferable that the total amount falls within the above-mentioned range.

<<Surface Active Agent>>

From the viewpoint of further improving coatability, the composition of the present invention may contain various surfactants. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used.

Since the composition contains a fluorine-based surfactant, the liquid properties (especially fluidity) when the coating liquid is prepared are further improved, and the uniformity of the coating thickness or the liquid-saving property can be further improved. That is, in the case of forming a film using a coating liquid applied with a composition containing a fluorine-based surfactant, the interfacial tension between the coated surface and the coating liquid decreases, and the wettability to the coated surface is improved , Improve the coatability to the coated surface. Therefore, it is possible to more preferably form a film with a small thickness unevenness and a uniform thickness.

The fluorine content in the fluorine-based surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. The fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid-saving properties, and its solubility in the composition is also good.

Specific examples of fluorine-based surfactants include Japanese Patent Laid-Open Surfactant described in paragraph number 0060 to paragraph number 0064 of 2014-41318 (corresponding to international publication WO2014/17669 manual paragraph number 0060 to paragraph number 0064), etc., Japanese Patent Laid-Open No. 2011-132503 Surfactant described in paragraph number 0117~paragraph number 0132, and these contents are incorporated into this specification. Commercial products of fluorine-based surfactants include, for example, Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac Megafac F479, Megafac F482, Megafac F554, Megafac F780 (manufactured by DIC (shares) above), Fluorad FC430, Flo Fluorad FC431, Fluorad FC171 (the above are manufactured by Sumitomo 3M (stock)), Surflon S-382, Surflon SC-101, Saffron Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon Surflon) SC-383, Surflon (Surflon) S393, Surflon (Surflon) KH-40 (the above are manufactured by Asahi Glass Co., Ltd.), PolyFox (PolyFox) PF636, PF656, PF6320, PF6520, PF7002 ( OMNOVA (manufactured by OMNOVA), etc.

Block polymers can also be used for fluorine-based surfactants. For example, Japan The compound described in Japanese Patent Laid-Open No. 2011-89090. As the fluorine-based surfactant, a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkoxy groups can also be preferably used. A fluorine-containing polymer compound which is a repeating unit of a (meth)acrylate compound (preferably an ethoxy group or a propoxy group). The following compounds can also be exemplified as the fluorine-based surfactant used in the present invention.

The weight average molecular weight of the compound is preferably 3,000 to 50,000, for example, 14,000. In the compound,% representing the ratio of repeating units is mass %.

In addition, the fluorine-based surfactant can also be used in a fluorine-containing polymer having an ethylenically unsaturated group in the side chain. As a specific example, Japanese Patent Laid-Open No. 2010-164965, Paragraph No. 0050 to Paragraph No. 0090 and Paragraph No. 0289 to Paragraph No. 0295 of the compounds described in Japanese Patent Laid-Open No. 2010-164965, for example, Mijia method manufactured by DIC Co., Ltd. (Megafac) RS-101, RS-102, RS-718K, RS-72-K, etc. As the fluorine-based surfactant, the compounds described in paragraph number 0015 to paragraph number 0158 of JP 2015-117327 A can also be used.

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerol propoxylates). , Glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether , Polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Sols Pass (Solsperse) 20000 (manufactured by Lubrizol (Stock) in Japan), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.), etc.

Examples of cationic surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No. 75, No. .90, No.95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yushang Co., Ltd.), etc.

Examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yushang Co., Ltd.), Sanded BL (manufactured by Sanyo Chemical Co., Ltd.), and the like.

Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone (Toray Silicone) DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone (Toray Silicone) SH8400 (the above is manufactured by Toray Dow Corning (stock)), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above is Momentive Performance Materials), KP341, KF6001, KF6002 (the above are manufactured by Shinetsu silicone Co., Ltd.), BYK 307, BYK 323, BYK 330 (above For BYK Chemie (manufactured by BYK Chemie), etc.

Only one type of surfactant may be used, or two or more types may be combined.

The content of the surfactant relative to the total solid content of the composition is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass.

<<Ultraviolet absorber>>

The composition of the present invention preferably contains an ultraviolet absorber.

Examples of the ultraviolet absorber include conjugated diene compounds and diketone compounds, and conjugated diene compounds are preferred. The conjugated diene compound is more preferably a compound represented by the following formula (UV-1).

In the formula (UV-1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² may be the same as each other. It may be different, and there is no case where hydrogen atoms are represented at the same time.

R ¹ and R ² can form a cyclic amino group together with the nitrogen atom to which ^{R 1} and R ^{2 are bonded.} As a cyclic amino group, a piperidinyl group, a morpholinyl group, a pyrrolidinyl group, a hexahydroazepine group, a piperazinyl group etc. are mentioned, for example.

Preferably, R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 5 carbon atoms.

R ³ and R ⁴ represent an electron withdrawing group. Here, the electron withdrawing group is an electron withdrawing group whose substituent constant σ _p value (hereinafter referred to as "σ _p value") of Hammett is 0.20 or more and 1.0 or less. Preferably, it is _{an electron withdrawing group having a σ p} value of 0.30 or more and 0.8 or less.

R ^{3 is} preferably a group selected from cyano, -COOR ⁵ , -CONHR ⁵ , -COR ⁵ , and -SO ₂ R ⁵ . R ^{4 is} preferably a group selected from cyano, -COOR ⁶ , -CONHR ⁶ , -COR ⁶ , and -SO ₂ R ⁶ . R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.

R ³ and R ^{4 are} preferably acyl group, carbamethanyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, amine The sulfonyl group is more preferably an acyl group, carbamethanyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, and sulfasulfonyl group. In addition, R ³ and R ⁴ may be bonded to each other to form a cyclic electron withdrawing group. Examples of the cyclic electron withdrawing group formed by bonding R ³ and R ^{4 to} each other include a 6-membered ring containing two carbonyl groups.

At least one of the aforementioned R ¹ , R ² , R ³ and R ⁴ may also be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. It can also be a copolymer with other monomers.

As specific examples of the ultraviolet absorber represented by the formula (UV-1), the following compounds can be cited. For the description of the substituent of the ultraviolet absorber represented by formula (UV-1), please refer to paragraph number 0024 to paragraph number 0033 of WO2009/123109 (corresponding U.S. Patent Application Publication No. 2011/0039195 [0040] ~[0059]), these contents are incorporated into this manual. For preferred specific examples of the compound represented by the formula (UV-1), refer to paragraph number 0034 to paragraph number 0037 of WO2009/123109 (corresponding U.S. Patent Application Publication No. 2011/0039195 Specification [0060]) The description of exemplified compound (1) to exemplified compound (14) is incorporated into this specification. As a commercial item of the ultraviolet absorber represented by Formula (UV-1), UV503 (made by Daito Chemical Co., Ltd.) etc. are mentioned, for example.

The diketone compound used as the ultraviolet absorber is preferably a compound represented by the following formula (UV-2).

In formula (UV-2), R ¹⁰¹ and R ¹⁰² each independently represent a substituent, and m1 and m2 each independently represent 0 to 4. Substituents include alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, Amino groups, amino groups, acylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, heteroaryloxycarbonylamino groups, sulfonylamino groups, sulfamsulfonylamino groups, carbamethanyl groups, Alkylthio, arylthio, heteroarylthio, alkylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylsulfinyl, arylsulfinyl, heteroarylsulfonyl Sulfonyl, ureido, phosphoamido, sulfhydryl, sulfo, carboxyl, nitro, hydroxylamine, sulfinic acid, hydrazine, imino, silyl, hydroxyl, halogen, cyano, etc., Preferred are alkyl and alkoxy.

The carbon number of the alkyl group is preferably 1-20. The alkyl group may be linear, branched, and cyclic, preferably linear or branched, and more preferably branched.

The carbon number of the alkoxy group is preferably 1-20. The alkoxy group may be linear, branched, and cyclic, preferably linear or branched, and more preferably branched.

Preferably, one of R ¹⁰¹ and R ¹⁰² is an alkyl group, and the other is a combination of an alkoxy group.

m1 and m2 independently represent 0 to 4, respectively. m1 and m2 are preferably independent The ground is 0~2, more preferably 0~1, particularly preferably 1.

Examples of the compound represented by formula (UV-2) include the following compounds.

As the ultraviolet absorber, Uvinul A (manufactured by BASF) can also be used. In addition, ultraviolet absorbers such as amino diene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, and triazine compounds can be used as ultraviolet absorbers. Specific examples include Japan The compound described in Patent Laid-Open No. 2013-68814. As the benzotriazole compound, MYUA series manufactured by Miyoshi Oils & Fats Co., Ltd. (Chemical Industry Daily, February 1, 2016) can also be used.

The content of the ultraviolet absorber is preferably 0.01% by mass to 10% by mass, and more preferably 0.01% by mass to 5% by mass relative to the total solid content of the composition of the present invention.

The ultraviolet absorber preferably contains 5 parts by mass to 100 parts by mass with respect to 100 parts by mass of the polymerizable compound. The upper limit is preferably 80 parts by mass or less, more preferably 60 parts by mass or less. The lower limit is preferably 10 parts by mass or more, more preferably 20 parts by mass or more.

<<Polymerization inhibitor>>

The composition of the present invention may contain a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the composition. Examples of polymerization inhibitors include compounds containing phenolic hydroxyl groups, N-oxide compounds, piperidine 1-oxy radical compounds, pyrrolidine 1-oxy radical compounds, and N-nitrosobenzene. Hydroxyamines, diazonium compounds, cationic dyes, compounds containing sulfide groups, compounds containing nitro groups, phosphorus compounds, lactone compounds, transition metal compounds (FeCl ₃ , CuCl ₂ etc.). In addition, among these compounds, it may be a composite compound in which a plurality of phenol skeletons or phosphorus-containing skeletons are present in the same molecule, and the structure exhibits a polymerization inhibitory function. For example, the compounds described in Japanese Patent Laid-Open No. 10-46035 and the like can also be preferably used. Specific examples of polymerization inhibitors include: hydroquinone, p-methoxyphenol, di-tertiary butyl p-cresol, gallic phenol, tertiary butyl catechol, benzoquinone, 4,4'-sulfur Substituted bis(3-methyl-6-tertiary butylphenol), 2,2'-methylene bis(4-methyl-6-tertiary butylphenol), N-nitrosophenylhydroxylamine Salt (ammonium salt, trivalent cerium salt, etc.). Among them, p-methoxyphenol is preferred.

The content of the polymerization inhibitor is preferably 0.01% by mass to 5% by mass relative to the total solid content of the composition.

The polymerization inhibitor is preferably contained in 0.001 part by mass to 1 part by mass relative to 100 parts by mass of the polymerizable compound. The upper limit is preferably 0.5 parts by mass or less, more preferably 0.2 parts by mass or less. The lower limit is preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more.

<<Other ingredients>>

The composition of the present invention may also contain sensitizers, hardening accelerators, fillers, thermal hardening accelerators, thermal polymerization inhibitors, plasticizers, and other auxiliary agents (for example, conductive Electrical particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension regulators, chain transfer agents, etc.). By appropriately containing these components, it is possible to adjust the stability of the targeted near-infrared cut filter and other optical filters, and properties such as film physical properties. For these components, refer to, for example, paragraph No. 0183 of Japanese Patent Laid-Open No. 2012-003225 (corresponding U.S. Patent Application Publication No. 2013/0034812 Specification [0237]), Japanese Patent Laid-Open No. 2008-250074 The paragraph number 0101~paragraph number 0104, paragraph number 0107~paragraph number 0109, etc., are incorporated into this specification. Moreover, as an antioxidant, a phenol compound, a phosphite compound, a thioether compound, etc. are mentioned. More preferably, it is a phenol compound with a molecular weight of 500 or more, a phosphite compound with a molecular weight of 500 or more, or a thioether compound with a molecular weight of 500 or more. These two or more types can also be mixed and used. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. As a preferable phenol compound, hindered phenol compound can be mentioned. Particularly preferred is a compound having a substituent at the position (ortho position) adjacent to the phenolic hydroxyl group. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tertiary butyl group. , Pentyl, isopentyl, third pentyl, hexyl, octyl, isooctyl, 2-ethylhexyl. In addition, a compound (antioxidant) having a phenol group and a phosphite group in the same molecule is also preferable. In addition, as the antioxidant, phosphorus-based antioxidants can also be preferably used. Examples of phosphorus antioxidants include those selected from tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2 ]Dioxaphosphapin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][ 1,3,2]dioxaphosphate At least one compound in the group consisting of hepeptin-2-yl)oxy)ethyl)amine and phosphite ethylbis(2,4-di-tert-butyl-6-methylphenyl) . These can be easily obtained as commercially available products, including: ADEKASTAB AO-20, ADEKASTAB AO-30, ADEKASTAB AO-40, ADEKASTAB AO-50, ADEKASTAB AO-50F, ADEKASTAB AO-60, ADEKASTAB AO-60G, Eddy ADEKASTAB AO-80, ADEKASTAB AO-330 (ADEKA (share)) and so on. The content of the antioxidant relative to the total solid content of the composition is preferably 0.01% by mass to 20% by mass, and more preferably 0.3% by mass to 15% by mass. There may be only one type of antioxidant, or two or more types. In the case of two or more types, it is preferable that the total amount falls within the above-mentioned range.

(Preparation method of composition)

The composition of the present invention can be prepared by mixing the ingredients.

When preparing the composition, each component can be blended at once, or it can be blended sequentially after being dissolved or dispersed in a solvent. In addition, there are no particular restrictions on the order of input or working conditions during deployment. For example, all the components can be dissolved or dispersed in a solvent at the same time to prepare a composition. If necessary, each component can also be prepared into two or more solutions or dispersions, and these can be mixed during use (during coating) To prepare a composition.

In addition, in the case of using a pigment containing a pigment as a near-infrared absorber, it is preferable to include a process of dispersing the pigment. In the process of dispersing the pigment, as a The mechanical force for the dispersion of the pigment includes compression, squeezing, impact, shear, cavitation, and the like.

Specific examples of these processes include: bead mills, sand mills, roller mills, ball mills, paint shakers, micro-jet homogenizers, high-speed impellers, sand grinders, and flow mixers. jet mixer), high-pressure wet micronization, ultrasonic dispersion, etc. In addition, in the pulverization of the pigment in a sand mill (bead mill), it is preferable to perform the treatment under conditions that increase the pulverization efficiency by using beads with a small diameter, increasing the filling rate of the beads, or the like. In addition, it is preferable to remove coarse particles by filtration, centrifugal separation, etc. after the pulverization treatment. In addition, the process of dispersing the pigment and the dispersing machine can preferably use "Dispersion Technology Encyclopedia, issued by Information Agency Co., Ltd., July 15, 2005" or "suspension (solid/liquid dispersion)" The center’s dispersion technology and actual industrial application, a comprehensive collection of materials, issued by the Publishing Department of the Management Development Center, October 10, 1978", the process and dispersion machine described in paragraph number 0022 of Japanese Patent Laid-Open No. 2015-157893. In addition, in the process of dispersing the pigment, the miniaturization treatment of the pigment by the salt milling step may also be performed. The raw materials, equipment, processing conditions, etc. used in the salt milling step can be those described in Japanese Patent Laid-Open No. 2015-194521 and Japanese Patent Laid-Open No. 2012-046629, for example.

When preparing the composition, for the purpose of removing foreign matter or reducing defects, it is preferable to filter by a filter. As the filter, if it is a filter that has been used for filtering purposes and the like since the past, it can be used without particular limitation. For example, the use of polytetrafluoroethylene (polytetrafluoroethylene, PTFE) and other fluororesin, nylon (examples Such as nylon-6, nylon-6, 6) and other polyamide resins, polyethylene, polypropylene (polypropylene, PP) and other polyolefin resins (including high-density, ultra-high molecular weight polyolefin resin) and other raw materials filters . Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore size of the filter is suitably about 0.01 μm to 7.0 μm, preferably about 0.01 μm to 3.0 μm, and more preferably about 0.05 μm to 0.5 μm. By setting it as this range, fine foreign matter can be reliably removed. In addition, it is also preferable to use a fibrous filter medium. As the fibrous filter material, for example, polypropylene fiber, nylon fiber, glass fiber, etc. can be cited. Specifically, SBP type series (SBP008 etc.) manufactured by Roki Techno (stock) and TPR type series (TPR002) can be used. , TPR005, etc.), SHPX series (SHPX003, etc.) filter cartridge (filter cartridge).

When using filters, different filters can also be combined. At this time, the filtration by the first filter may be performed only once, or may be performed twice or more.

In addition, it is also possible to combine first filters having different pore diameters within the above-mentioned range. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, available from Pall Co., Ltd. (DFA4201NXEY, etc.), Advantec Toyo (stock), Nihon Entegris (stock) ( Choose from a variety of filters provided by the original Japanese Mykrolis (stock) or Kitz Microfilter (stock).

As the second filter, a filter formed of the same material as the first filter can be used.

For example, the filtration with the first filter can be performed only in the dispersion liquid, and in the mixing After the other ingredients, perform the second filtration.

For example, in the case of forming a film by coating, the viscosity (23°C) of the composition of the present invention is preferably at 1 mPa. s~3000mPa. The range of s. The lower limit is preferably 3mPa. s or more, more preferably 5mPa. s above. The upper limit is preferably 2000 mPa. s or less, more preferably 1000mPa. s or less.

The composition of the present invention can also be used for a near-infrared cut filter on the light-receiving side of a solid-state image sensor (for example, a near-infrared cut filter for a wafer-level lens, etc.), and the back side of a solid-state image sensor (and the light-receiving side). It is the near-infrared cut filter on the opposite side). In addition, the composition of the present invention may be directly applied to an image sensor to form a coating film and used.

Since the composition of the present invention can be supplied in a coated state, it is possible to easily form a near-infrared cut filter at a desired member or position of the solid-state imaging element.

In addition, the composition of the present invention can also be applied to a glass substrate or a layer containing copper.

The film obtained by using the composition of the present invention preferably has a maximum absorption wavelength in the range of 700 nm to 1000 nm, and the ratio of the absorbance Amax at the maximum absorption wavelength to the absorbance A550 at a wavelength of 550 nm, that is, the absorbance Amax/ The absorbance A550 is 50~500.

In addition, the maximum absorption wavelength of the film is more preferably in the range of 720 nm to 980 nm, and more preferably in the range of 740 nm to 960 nm. In addition, the absorbance Amax/absorbance A550 of the film is more preferably 70 to 450, and still more preferably 100 to 400.

In addition, the film thickness of the film obtained using the composition of the present invention is preferably 20 μm or less, more preferably 10 μm or less, and still more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more. In at least one of the above-mentioned film thickness ranges, the ratio of absorbance Amax/absorbance A550 to absorbance A550 is preferably 50 to 500.

The transmittance of the film obtained using the composition of the present invention and the near-infrared cut filter described later preferably satisfies at least one of the following conditions (1) to (4), and more preferably satisfies (1) to (4) ) All conditions.

(1) The transmittance at a wavelength of 400 nm is preferably 70% or more, more preferably 80% or more, still more preferably 85% or more, particularly preferably 90% or more.

(2) The transmittance at a wavelength of 500 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more.

(3) The transmittance at a wavelength of 600 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, particularly preferably 95% or more.

(4) The transmittance at a wavelength of 650 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, particularly preferably 95% or more.

The film thickness of the film obtained using the composition of the present invention and the near-infrared cut filter described later is 20 μm or less, and the transmittance in all ranges of wavelengths from 400 nm to 650 nm is preferably 70% or more, more preferably 80% or more, More preferably, it is 90% or more. In addition, the transmittance at at least one point in the wavelength range of 700 nm to 1000 nm is preferably 20% or less.

<Optical Filter>

Next, the optical filter of the present invention will be described. The optical filter of the present invention is obtained by using the composition of the present invention described above. The optical filter can be preferably used as a near-infrared cut filter and an infrared transmission filter. In addition, optical filters can also be used as infrared shielding filters. In addition, in the present invention, the so-called near infrared cut filter refers to a filter that transmits light of a wavelength in the visible light region (visible light) and shields at least a part of light of a wavelength in the near infrared region (near infrared). In addition, in the present invention, the term "infrared transmission filter" refers to a filter that blocks light of a wavelength in the visible light region and transmits at least a part of light of a wavelength in the near-infrared region (near infrared).

When the optical filter of the present invention is used as an infrared transmission filter, the infrared transmission filter includes, for example, a filter that blocks visible light and transmits light having a wavelength of 900 nm or more. When the optical filter of the present invention is used as an infrared transmission filter, it is preferable to have a filter including a layer of a colored material that shields visible light in addition to the layer using the composition of the present invention.

The film thickness of the film containing the composition of this invention in an optical filter can be adjusted suitably according to the objective. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and still more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more.

When using the optical filter of this invention as a near-infrared cut filter, you may have an anti-reflection film, an ultraviolet absorption film, etc. other than the film containing the composition of this invention. As the ultraviolet absorbing film, for example, reference can be made to paragraph numbers 0040 to 0070 of WO2015/099060, and paragraph numbers. The absorbent layer described in No. 0119 to Paragraph No. 0145 is incorporated into this specification. As the anti-reflection film, a laminate in which a high-refractive layer and a low-refractive layer are alternately laminated (for example, a dielectric multilayer film, etc.) can be cited. The spectral characteristics of the anti-reflection film can be appropriately selected according to the wavelength of the light source, the spectral characteristics of the optical filter, and the like. By combining a film containing the composition of the present invention and an anti-reflection film, it is also possible to block infrared rays in a wide area. For the details of the anti-reflection film, reference can be made to the description of paragraph number 0255 to paragraph number 0259 of JP 2014-41318 A, and this content is incorporated into this specification.

The optical filter of the present invention can be used in various devices such as solid-state imaging elements such as charge coupled devices (CCD) or complementary metal oxide film semiconductor (CMOS) devices, or infrared sensors and image display devices. In addition, the optical filter of the present invention can be used for lenses that have a function of absorbing or blocking near infrared rays (lenses for cameras such as digital cameras, mobile phones, or car cameras, optical lenses such as f-theta lenses, reading lenses, etc.) and semiconductor light receiving Optical filters for components, near-infrared absorbing films or near-infrared absorbing plates that block infrared rays for energy conservation, agricultural coating films for the selective use of sunlight, recording media that use near-infrared absorbing heat, Near-infrared filters for electronic equipment or photographs, protective glasses, sunglasses, infrared cut filters, optical text reading and recording filters, filters for preventing copying of confidential documents, electronic photo photosensitive bodies, etc. It is also useful as a noise cut filter for CCD cameras and a filter for CMOS image sensors.

In addition, the optical filter of the present invention has pixels and options using the composition of the present invention (preferably a composition further comprising a colored material that shields visible light). Aspects of pixels from red, green, blue, magenta, yellow, cyan, black, and colorless are also preferable.

<Laminated body>

The laminate of the present invention has a near-infrared cut filter using the radiation-sensitive composition of the present invention and a color filter containing a color colorant. The near-infrared cut filter and the color filter in the laminate of the present invention may or may not be adjacent to each other in the thickness direction. When the near-infrared cut filter and the color filter are not adjacent to each other in the thickness direction, the near-infrared cut filter may be formed on a substrate different from the base on which the color filter is formed, or the near-infrared cut filter may be cut in the near-infrared Between the filter and the color filter, there are other members constituting the solid-state imaging element (for example, a microlens, a planarization layer, etc.).

<Pattern Formation Method>

Next, the pattern forming method of the present invention will be described. The pattern forming method of the present invention includes: a step of forming a radiation-sensitive composition layer on a support using the radiation-sensitive composition of the present invention; a step of exposing the radiation-sensitive composition layer in a pattern; and The step of developing and removing the exposed part to form a pattern. Hereinafter, each step will be described in detail.

<<Steps of forming a radiation-sensitive composition layer>>

In the step of forming the radiation-sensitive composition layer, the radiation-sensitive composition of the present invention is used to form the radiation-sensitive composition layer on the support.

Examples of the support include substrates containing materials such as glass, silicon, polycarbonate, polyester, aromatic polyamide, polyimide, and polyimide. In addition, a support for a solid-state imaging element in which a solid-state imaging element (light-receiving element) such as CCD or CMOS is provided on a substrate can be used.

The pattern may be formed on the surface side (front surface) of the solid-state imaging element substrate on which the solid-state imaging element is formed, or may be formed on the surface side (rear surface) where the solid-state imaging element is not formed. On the support, if necessary, an undercoat layer can also be provided to improve the adhesion with the upper layer, prevent the diffusion of substances, or realize the flattening of the substrate surface.

As a method of applying the radiation-sensitive composition of the present invention to the support, a known method can be used. Examples include: drop method (drop casting); slit coating method; spray method; roll coating method; spin coating method; cast coating method; slit and spin method ; Pre-wet method (for example, the method described in Japanese Patent Laid-Open No. 2009-145395); inkjet (for example, on-demand method, piezo method, thermal method), Various printing methods such as nozzle jetting, such as printing, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc.; transfer methods using molds, etc.; nanoimprinting methods, etc. The application method by inkjet is not particularly limited. For example, "Extended. Inkjet Used-Unlimited Possibilities Seen in Patent-Issued in February 2005, Sumibe Techno Research" The method described in the Japanese Patent Publication shown (especially pages 115 to 133), or Japanese Patent Laid-Open No. 2003-262716, Japanese Patent Laid-Open No. 2003-185831, and Japanese Patent Laid-Open No. 2003-261827 , Japanese Patent Application Publication No. 2012-126830, Japanese Patent Application Publication No. 2006-169325, etc.

The radiation-sensitive composition layer formed on the support can be dried (pre- bake). When the pattern is formed by a low-temperature process, pre-baking may not be performed. In the case of pre-baking, the pre-baking temperature is preferably 150°C or lower, more preferably 120°C or lower, and still more preferably 110°C or lower. The lower limit may be 50°C or higher, or 80°C or higher, for example. The pre-baking time is preferably 10 seconds to 300 seconds, more preferably 40 seconds to 250 seconds, and still more preferably 80 seconds to 220 seconds. Drying can be carried out using a hot plate, oven, etc.

<<Steps to Exposure>>

Next, the radiation-sensitive composition layer formed on the support is exposed in a pattern. For example, by using an exposure device such as a stepper to expose the radiation-sensitive composition layer through a mask having a predetermined mask pattern, pattern exposure can be performed. Thereby, the exposed part can be hardened.

As the radiation (light) that can be used in exposure, ultraviolet rays such as g-rays and i-rays (especially i-rays) can be preferably used. The irradiation amount (exposure amount) is, for example, preferably 0.03 J/cm ² to 2.5 J/cm ² , and more preferably ^{0.05 J/cm 2} to 1.0 J/cm ² .

The oxygen concentration during exposure can be appropriately selected. In addition to exposure in the atmosphere, exposure can be performed in a low-oxygen environment with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, and substantially no oxygen). It can also be exposed in a high-oxygen environment with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, and 50% by volume). Further, exposure illuminance can be appropriately set, typically ^{1000W / m 2 ~ 100000W / m} 2 ( ^{e.g., 5000W / m 2, 15000W /} m 2, 35000W / m 2) selected from the range. The oxygen concentration and the exposure illuminance can be combined with appropriate conditions. For example, an oxygen concentration of 10% by ^{volume and an illuminance of 10,000 W/m 2} , an oxygen concentration of 35% by volume and an illuminance of 20,000 W/m ² can be set.

<<Development Step>>

Next, the unexposed part is developed and removed to form a pattern. The development and removal of the unexposed part can be performed using a developer. Thereby, the radiation-sensitive composition of the unexposed part in the exposure step is eluted into the developing solution, and only the light-hardened part remains.

As the developer, an organic alkaline developer that does not damage the solid-state imaging element or circuit of the substrate or the like is desirable.

The temperature of the developer is preferably 20°C to 30°C, for example. The development time is preferably 20 seconds to 180 seconds. In addition, in order to improve the residue removal performance, the following steps may be repeated several times: the developer is shaken off every 60 seconds, and then a new developer is supplied.

The alkaline agent used in the developer includes, for example, ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, Tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, Piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene and other organic alkaline agents. As the developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water can be preferably used. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 1% by mass.

In addition, an inorganic alkaline agent can also be used in the developer. As the inorganic alkaline agent, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, etc. are preferred.

In addition, surfactants can also be used in the developer. As an example of surfactant Examples include the surfactants described in the composition of the present invention, and nonionic surfactants are preferred.

In the case of using a developer containing an alkaline aqueous solution, it is preferable to wash (rinse) with pure water after development.

It is also possible to perform heat treatment (post-baking) after development and drying. Post-baking is a heat treatment after development to completely harden the film. In the case of post-baking, the post-baking temperature is preferably 100°C to 240°C, for example. From the viewpoint of film hardening, it is more preferably 200°C to 230°C. In addition, when an organic electroluminescence (Electroluminescence) element is used as a light source or when the photoelectric conversion film of an image sensor is composed of organic materials, the post-baking temperature is preferably 150°C or lower. It is more preferably 120°C or lower, still more preferably 100°C or lower, and particularly preferably 90°C or lower. The lower limit can be set to 50°C or higher, for example. A heating mechanism such as a heating plate, a convection oven (hot air circulation type dryer), a high-frequency heater, etc. can be used to post-bake the developed film in a continuous or batch manner so as to meet the above-mentioned conditions.

In addition, the pattern forming method of the present invention may further have a step of exposing after developing and removing the unexposed part (after developing) (hereinafter, the exposure after developing is also referred to as post-exposure). In the case of using a radiation-sensitive composition containing an oxime compound and an α-aminoketone compound as a photopolymerization initiator, it is preferable to perform post-exposure. By exposing the radiation-sensitive composition layer in two stages before and after pattern formation, the radiation-sensitive composition can be properly cured in the initial exposure (exposure before patterning), and can be used in the next exposure During (exposure after patterning), the radiation-sensitive composition is substantially hardened as a whole. As a result, even if the post-baking temperature is Below 180°C, the curability of the radiation-sensitive composition can also be improved.

In the case of exposure in two stages, post-exposure may be followed by post-baking. The post-baking temperature is preferably 100°C to 240°C, for example.

<Solid-state imaging device>

The solid-state imaging element of the present invention has the optical filter of the present invention. The configuration of the solid-state imaging element of the present invention is not particularly limited as long as it has the optical filter of the present invention and functions as a solid-state imaging element. For example, the following configurations can be cited.

The solid-state imaging element has the following structure: a support body has a plurality of photodiodes (photodiodes) constituting a light receiving region of the solid-state imaging element and a transmission electrode including polysilicon, etc., and only two photodiodes are provided on the photodiode and the transmission electrode. A light-shielding film containing tungsten, etc. where the light-receiving portion of the polar body is opened, and a device protection film containing silicon nitride, etc., formed to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode is provided on the light-shielding film to protect the device The film has the film of the present invention on the film.

Furthermore, it may be a configuration having a light-concentrating mechanism (for example, a micro lens, etc., the same below) on the device protective film and under the near-infrared cut filter (on the side close to the support), or on the near-infrared cut filter It has a condensing mechanism, etc. In addition, in the solid-state imaging device, the color filter may have a structure in which a cured film forming pixels of each color is buried in a space partitioned into, for example, a lattice shape by a partition wall. In this case, the partition wall preferably has a low refractive index with respect to each color pixel. As an example of an imaging device having such a structure, the devices described in Japanese Patent Laid-Open No. 2012-227478 and Japanese Patent Laid-Open No. 2014-179577 can be cited.

<Image display device>

The optical filter of the present invention can also be used in image display devices such as liquid crystal display devices or organic electroluminescence (organic EL) display devices. For example, by using together with each colored pixel (such as red, green, blue), it can be used to block the backlight of the image display device (such as white light emitting diode (White LED (Light Emitting Diode))). The included infrared light is used for the purpose of preventing malfunctions of peripheral devices, or for the purpose of forming each colored display pixel and infrared pixel.

The definition of image display devices or the details of image display devices, for example, are described in "Electronic Display Devices (by Sasaki Akio, Industrial Research Council (Stock), issued in 1990)" and "Display Devices (by Ibuki Junsho, Industrial Books (shares), issued in 1989)" etc. In addition, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, Industrial Research Council (Stock), Issued in 1994)". The liquid crystal display device to which the present invention is applicable is not particularly limited. For example, it can be applied to various types of liquid crystal display devices described in the "Next Generation Liquid Crystal Display Technology".

The image display device may have a white organic EL element. The white organic EL device preferably has a tandem structure. Regarding the tandem structure of organic EL elements, published in Japanese Patent Laid-Open No. 2003-45676, edited by Akoyoshi Mikami, "The front line of organic EL technology development-high brightness, high precision, long life, and proprietary technology collection -", Technical Information Association, pages 326-328, recorded in 2008 etc. The spectrum of the white light emitted by the organic EL element is preferably one having a strong maximum emission peak in the blue region (430nm-485nm), the green region (530nm-580nm), and the yellow region (580nm-620nm). More preferably, in addition to these luminescence peaks, those having the largest luminescence peak in the red region (650 nm-700 nm) are further preferred.

<Infrared Sensor>

The infrared sensor of the present invention has the optical filter of the present invention. The structure of the infrared sensor is not particularly limited as long as it has the optical filter of the present invention and functions as an infrared sensor.

Hereinafter, an embodiment of the infrared sensor of the present invention will be described using drawings.

In FIG. 1, reference numeral 110 is a solid-state imaging element. The imaging area provided on the solid-state imaging element 110 has a near-infrared cut filter 111 and an infrared transmission filter 114. In addition, a color filter 112 is laminated on the near-infrared cut filter 111. A microlens 115 is arranged on the incident light hν side of the color filter 112 and the infrared transmission filter 114. A planarization layer 116 is formed to cover the microlens 115. The near-infrared cut filter 111 can be formed using the composition of the present invention.

The color filter 112 is a color filter that transmits and absorbs light of a specific wavelength in the visible light region and is formed with pixels, and is not particularly limited, and a conventionally known color filter for pixel formation can be used. For example, a color filter formed with red (R), green (G), and blue (B) pixels can be used. For example, the description of paragraph number 0214 to paragraph number 0263 of JP 2014-043556 A can be referred to, and the content can be incorporated into this specification.

The infrared transmission filter 114 selects its characteristics according to the emission wavelength of the infrared LED described later. For example, in the case where the emission wavelength of an infrared LED is 850nm In this case, the maximum light transmittance in the thickness direction of the film of the infrared transmission filter 114 in the wavelength range of 400 nm to 650 nm is preferably 30% or less, more preferably 20% or less, and still more preferably 10% or less. Preferably, it is 0.1% or less. The transmittance preferably satisfies the aforementioned conditions in the entire wavelength range of 400 nm to 650 nm. The maximum value in the wavelength range of 400 nm to 650 nm is usually 0.1% or more.

The minimum value of the light transmittance in the thickness direction of the film of the infrared transmission filter 114 in the wavelength range of 800 nm or more (preferably 800 nm to 1300 nm) is preferably 70% or more, more preferably 80% or more, and still more preferably 90 %above. The transmittance preferably satisfies the above-mentioned condition in a part of the wavelength range of 800 nm or more, and preferably satisfies the above-mentioned condition at a wavelength corresponding to the emission wavelength of the infrared LED. The minimum value of the light transmittance in the wavelength range of 900 nm to 1300 nm is usually 99.9% or less.

The film thickness of the infrared transmission filter 114 is preferably 100 μm or less, more preferably 15 μm or less, still more preferably 5 μm or less, and particularly preferably 1 μm or less. The lower limit is preferably 0.1 μm. If the film thickness is in the above range, it can be made into a film that satisfies the above-mentioned spectral characteristics.

The methods for measuring the spectral characteristics, film thickness, and the like of the infrared transmission filter 114 are shown below.

Regarding the film thickness, a stylus-type surface profile measuring device (DEKTAK150 manufactured by ULVAC Co., Ltd.) was used to measure the dried substrate with the film.

The spectroscopic properties of the film are values obtained by measuring the transmittance in a wavelength range of 300 nm to 1300 nm using an ultraviolet-visible-near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Co., Ltd.).

The infrared transmission filter 114 having the above-mentioned spectral characteristics can be formed using a composition containing a colored material that shields visible light. The details of the colored material that shields visible light are the same as those described in the composition of the present invention.

In addition, for example, when the emission wavelength of the infrared LED is 940 nm, the infrared transmission filter 114 preferably has a maximum transmittance of 20% or less in the thickness direction of the film in the range of wavelengths from 450 nm to 650 nm. The light transmittance at a wavelength of 835 nm in the direction is 20% or less, and the light transmittance in the thickness direction of the film has a minimum value of 70% or more in the range of wavelengths from 1000 nm to 1300 nm.

The infrared transmission filter 114 having the above-mentioned spectral characteristics can be manufactured using a composition including a colored material that shields visible light and a near-infrared absorbing compound having a maximum absorption wavelength in the range of 750 nm to 950 nm. The details of the colored material that shields visible light are the same as those described in the composition of the present invention. Examples of the near-infrared absorbing compound include the near-infrared absorbing compounds described in the composition of the present invention.

[Example]

Hereinafter, examples are given to explain the present invention more specifically. The materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "%" and "parts" are quality standards. In the following structural formulae, Me represents a methyl group and Ph represents a phenyl group.

<Method of measuring acid value>

Dissolve the measurement sample in a mixed solvent of tetrahydrofuran/water=9/1 (mass ratio) In addition, a potentiometric titration device (trade name: AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.) was used to neutralize the obtained solution with a 0.1 mol/L sodium hydroxide aqueous solution at 25°C. The inflection point of the titration pH curve is set as the titration end point, and the acid value is calculated by the following formula.

A=56.11×Vs×0.5×f/w

A: Acid value (mgKOH/g)

Vs: the amount of 0.1mol/L sodium hydroxide aqueous solution needed for titration (mL)

f: The titration rate of 0.1mol/L sodium hydroxide aqueous solution

w: The mass of the sample to be measured (g) (conversion of solid content)

<Measurement of Amine Value>

Dissolve the measurement sample in acetic acid, and use a potentiometric titration device (trade name: AT-510, manufactured by Kyoto Electronics Co., Ltd.) at 25° C. to obtain the result with a 0.1 mol/L perchloric acid/acetic acid solution pair The solution is neutralized and titrated. The inflection point of the titration pH curve is set as the titration end point, and the amine value is calculated by the following formula.

B=56.11×Vs×0.1×f/w

B: Amine value (mgKOH/g)

Vs: The usage amount of 0.1mol/L perchloric acid/acetic acid solution required for titration (mL)

f: The titer of 0.1mol/L perchloric acid/acetic acid solution

w: The mass of the sample to be measured (g) (conversion of solid content)

<Measurement of weight average molecular weight>

For the measurement of the weight average molecular weight of the resin, HPC-8220GPC (manufactured by TOSOH Co., Ltd.) was used as the measuring device, TSKguardcolumn SuperHZ-L was used as the guard column, and TSKgel SuperHZM-M, TSKgel SuperHZ4000, TSKgel SuperHZ3000 and TSKgel SuperHZ2000 directly connected as the column, set the column temperature to 40℃, and inject 10μL of tetrahydrofuran solution with a sample concentration of 0.1% by mass, and use it as the dissolution solvent at a flow rate of 0.35mL per minute The tetrahydrofuran is flowing, and the sample peak is detected using a differential refractive index (RI) detection device, and the calculation is performed using a calibration curve made using standard polystyrene.

<Preparation of dispersion>

(Dispersion 1)

7.8 parts by mass of compound 1, 1.5 parts by mass of pigment derivative 1, 5.6 parts by mass of dispersant 1, 85 parts by mass of propylene glycol monomethyl ether acetate (Propyleneglycol monomethyl ether acetate, PGMEA), And 200 parts by mass of zirconia beads with a diameter of 0.5mm for 30 minutes, and then filtered using DFA4201NXEY (0.45μm nylon filter) manufactured by Pall (Stock), and then oxidized by filtration. The zirconium beads were separated to prepare a dispersion liquid 1.

Compound 1: The following compound

[化65]

Pigment Derivative 1: The following compound

Dispersant 1: Resin of the following structure (acid value=32.3 mgKOH/g, amine value=45.0 mgKOH/g, weight average molecular weight=21000). The numerical value attached to the main chain represents the molar ratio of the repeating unit, and the numerical value attached to the side chain represents the number of the repeating unit. Dispersant 1 is also an alkali-soluble resin.

[化67]

(Dispersion 2)

7.8 parts by mass of compound 2, 1.5 parts by mass of pigment derivative 1, 5.6 parts by mass of dispersant 1, 85 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), and 200 parts by mass of After the zirconia beads with a diameter of 0.5mm were dispersed for 30 minutes, they were filtered using DFA4201NXEY (0.45μm nylon filter) manufactured by Pall Co., Ltd., and then the zirconia beads were separated by filtration. Dispersion 2.

Compound 2: The following compound

(Dispersion 3)

7.8 parts by mass of compound 3, 1.5 parts by mass of pigment derivative 1, 5.6 parts by mass of dispersant 1, and 85 parts by mass of propylene glycol monomethyl ether were applied by a paint shaker (PGME), and 200 parts by mass of zirconia beads with a diameter of 0.5mm for 30 minutes, and then filtered using DFA4201NXEY (0.45μm nylon filter) manufactured by Pall, Japan, and then borrowed The zirconia beads were separated by filtration to prepare dispersion 3.

Compound 3: The following compound

(Dispersion 4)

7.8 parts by mass of compound 4 (IRA884, manufactured by Exiton), 5.6 parts by mass of dispersant 1, 85 parts by mass of PGMEA, and 200 parts by mass of zirconia with a diameter of 0.5 mm After the beads were subjected to a dispersion treatment for 30 minutes, they were filtered using DFA4201NXEY (0.45 μm nylon filter) manufactured by Pall Co., Ltd., and then the zirconia beads were separated by filtration to prepare a dispersion liquid 4.

(Dispersion 5)

7.8 parts by mass of compound 5 (SDO-C33, manufactured by Yumoto Chemical Industry Co., Ltd.), 5.6 parts by mass of dispersant 1, 85 parts by mass of PGMEA, and 200 parts by mass of 0.5mm diameter After the zirconia beads were subjected to a 30-minute dispersion treatment, they were filtered using DFA4201NXEY (0.45 μm nylon filter) manufactured by Pall Co., Ltd., and then the zirconia beads were separated by filtration to prepare a dispersion liquid 5.

(Dispersion 6)

7.8 parts by mass of compound 6 (SMP-388, manufactured by Hayashibara Co., Ltd.), 5.6 parts by mass of dispersant 1, 85 parts by mass of PGMEA, and 200 parts by mass of zirconia beads with a diameter of 0.5 mm were applied by a paint shaker After performing the dispersion treatment for 30 minutes, filtration was performed using DFA4201NXEY (0.45 μm nylon filter) manufactured by Pall Co., Ltd., and then the zirconia beads were separated by filtration to prepare a dispersion liquid 6.

(Dispersion 7)

7.8 parts by mass of compound 7, 1.5 parts by mass of pigment derivative 2, 5.6 parts by mass of dispersant 2, 85 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), and 200 parts by mass of After the zirconia beads with a diameter of 0.5mm were dispersed for 30 minutes, they were filtered using DFA4201NXEY (0.45μm nylon filter) manufactured by Pall Co., Ltd., and then the zirconia beads were separated by filtration. Dispersion 7.

Compound 7: The following compound

[化70]

Pigment Derivative 2: The following compound

Dispersant 2: Resin of the following structure (acid value=57mgKOH/g, weight average molecular weight=33000). The numerical value attached to the main chain represents the molar ratio of the repeating unit, and the numerical value attached to the side chain represents the number of the repeating unit. Dispersant 2 is also an alkali-soluble resin.

[化72]

(Dispersion 8)

YMS-01A-2 (manufactured by Sumitomo Metal Mining Co., Ltd., dispersion of tungsten fine particles) was used as the dispersion liquid 8.

(Dispersion 9)

7.8 parts by mass of compound 9 (IRG-068, manufactured by Nippon Kayaku Co., Ltd.), 5.6 parts by mass of dispersant 1, 85 parts by mass of PGMEA, and 200 parts by mass of 0.5 mm in diameter were oxidized by a paint shaker After the zirconium beads were subjected to a 30-minute dispersion treatment, they were filtered using DFA4201NXEY (0.45 μm nylon filter) manufactured by Pall Co., Ltd., and then the zirconium oxide beads were separated by filtration to prepare dispersion 9.

(Dispersion 10)

7.8 parts by mass of compound 10 (IRA868, manufactured by Exiton), 5.6 parts by mass of dispersant 1, 85 parts by mass of PGMEA, and 200 parts by mass of zirconia with a diameter of 0.5 mm After the beads were subjected to a dispersion treatment for 30 minutes, they were filtered using DFA4201NXEY (0.45 μm nylon filter) manufactured by Pall Co., Ltd., and then the zirconia beads were separated by filtration to prepare a dispersion liquid 10.

<Preparation of Radiation Sensitive Composition>

After mixing and stirring the materials shown in the following table in the proportions (parts by mass) shown below, they were filtered with a nylon filter with a pore size of 0.45 μm (manufactured by Pall Co., Ltd., DFA4201NXEY) To prepare a radiation-sensitive composition. In addition, in the following tables, the M/B ratio is the mass ratio of the radical polymerizable compound to the resin having an acid group (radical polymerizable compound/resin having an acid group).

[Table 1]

The materials shown in the table are as follows.

(Radical polymerizable compound)

M-510: Aronix M-510 (manufactured by Toagosei Co., Ltd., polyacid modified acrylic oligomer)

M-305: Aronix M-305 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, containing 55 mass% to 63 mass% of pentaerythritol triacrylate)

(Alkali-soluble resin)

Resin A: A resin having the following structure (acid value = 101 mgKOH/g, weight average molecular weight = 38900). The numerical value attached to the main chain represents the mass ratio of the repeating unit, and the numerical value attached to the side chain represents the number of the repeating unit.

Resin B: Acrycure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.)

(Photo-radical polymerization initiator)

C-1: IRGACURE OXE02 (manufactured by BASF)

C-2: IRGACURE 369 (manufactured by BASF)

C-3: The following compounds

C-4: B-CIM (manufactured by Hodogaya Chemical Industry Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'- Biimidazole)

C-5: IRGACURE OXE01 (manufactured by BASF)

(Ultraviolet absorber)

D-1: The following compounds

D-2: The following compound

[化76]

D-3: Uvinul A (manufactured by BASF)

(Chain transfer agent)

E-1: The following compounds

E-2: Sanceler M (manufactured by Sanxin Chemical Industry Co., Ltd., 2-mercaptobenzothiazole)

E-3: Karenz MT BD1 (manufactured by Showa Denko Co., Ltd., 1,4-bis(3-mercaptobutoxy)butane)

(Surfactant)

F-1: The following mixture (weight average molecular weight = 14000, the% representing the proportion of repeating units is mass %)

[化78]

(Polymerization inhibitor)

G-1: p-Methoxyphenol

(Solvent)

PGMEA: Propylene Glycol Monomethyl Ether Acetate

PGME: Propylene Glycol Monomethyl Ether

BDGAC: Diethylene glycol monobutyl ether acetate

<evaluation>

(Rectangularity)

Using the spin coating method, each radiation-sensitive composition was coated on a silicon wafer with a primer layer so that the film thickness after coating became 0.7μm, and then heated on a hot plate at 100°C for 2 minutes. And a radiation-sensitive composition layer is obtained.

Then, using an i-ray stepping exposure device FPA-3000i5+ (manufactured by Canon (Canon) Co., Ltd.), the obtained radiation-sensitive composition layer was exposed through a mask with a 1.1 μm square Bayer pattern ( The amount of exposure is the optimal amount of exposure that selects the line width to be 1.1μm).

Then, tetramethylammonium hydroxide (Tetramethylammonium hydroxide, TMAH) 0.3% by mass aqueous solution was used, and the sensitivity after exposure was measured at 23°C. The radioactive composition layer was developed in a liquid-in-coup mode for 60 seconds. After that, rinsing is performed by rotating spray, and then a pattern is obtained by washing with pure water.

A scanning electron microscope (Scanning Electron Microscope, SEM) was used to observe (magnification: 25000 times) the cross section (pixel side wall) of the pattern portion and evaluate the rectangularity. The results are shown in the following table.

4: The angle of the side wall of the pixel is 85° or more and less than 95°

3: The angle of the pixel side wall is 80° or more and less than 85°, or 95° or more and less than 100°

2: The angle of the side wall of the pixel is 70° or more and less than 80°, or 100° or more and less than 110°

1: The angle of the side wall of the pixel is less than 70°, or 110° or more

<Remaining residue>

Using the spin coating method, each radiation-sensitive composition was coated on a silicon wafer with a primer layer so that the film thickness after coating became 0.7μm, and then heated on a hot plate at 100°C for 2 minutes. And a radiation-sensitive composition layer is obtained.

Then, using the i-ray stepping exposure device FPA-3000i5+ (manufactured by Canon (Canon) Co., Ltd.), the obtained radiation-sensitive composition layer was exposed with a 1.1μm square Bayer pattern (exposure amount). It is to select the optimal exposure amount for the line width to be 1.1μm).

Then, using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), the exposed radiation-sensitive composition layer was subjected to liquid-over development at 23° C. for 60 seconds. Afterwards, it is rinsed by rotating spray, and then rinsed by pure water to obtain pattern.

The amount of residue remaining on the base of the obtained pattern was evaluated by the binarization process of the image. The results are shown in the following table.

3: The amount of residue is less than 1% of the total area of the substrate

2: The amount of residue is 1%~3% of the total area of the substrate

1: The amount of residue exceeds 3% of the total area of the substrate

(Spectroscopic characteristics)

Using the spin coating method, each radiation-sensitive composition of the obtained Examples and Comparative Examples was coated on a glass wafer so that the film thickness after coating became 0.7μm, and then it was heated at 100°C on a hot plate. Heat for 2 minutes. Next, an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Co., Ltd.) was used to perform exposure ^{at 1000 mJ/cm 2.} Furthermore, it heated at 220 degreeC for 5 minutes on a hotplate, and formed the radiation-sensitive composition layer. For the substrate on which the radiation-sensitive composition layer is formed, a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies) is used to obtain the maximum absorption wavelength, the absorbance Amax and the wavelength at the maximum absorption wavelength The absorbance A550 at 550 nm, and the ratio of the absorbance Amax at the maximum absorption wavelength to the absorbance A550 at the wavelength 550 nm (absorbance Amax/absorbance A550) was calculated.

5: The ratio of absorbance Amax/absorbance A550 is 100~500, and the maximum absorption wavelength is 700nm or more and 1000nm or less

4: The ratio of absorbance Amax/absorbance A550 is 50 or more and less than 100, and the maximum absorption wavelength is 700 nm or more and 1000 nm or less

3: Absorbance Amax/Absorbance A550 ratio is 20 or more and less than 50, and the maximum absorption wavelength is 700nm or more and 1000nm or less

2: The ratio of absorbance Amax/absorbance A550 is less than 20, and the maximum absorption wavelength is 700nm or more and 1000nm or less

1: The ratio of absorbance Amax/absorbance A550 is less than 20, and the maximum absorption wavelength is less than 700nm or more than 1000nm

As shown in the table, the examples have excellent spectral characteristics and rectangularity, and can form a pattern with good infrared shielding properties and excellent rectangularity. Furthermore, residue residue can be suppressed. In addition, when the cured film using the radiation-sensitive composition of the example was incorporated into the solid-state imaging device, the infrared shielding property was high, and the visibility of the image was excellent.

In contrast, the comparative example is inferior in at least one of rectangularity and spectral characteristics.

(Example 101)

Using the spin coating method, the radiation sensitive composition of Example 1 was coated on a silicon wafer with an undercoating layer so that the film thickness after coating became 0.7 μm, and then it was applied on a hot plate at 100°C for 2 Minute heating to obtain a radiation-sensitive composition layer.

Then, using an i-ray stepping exposure device FPA-3000i5+ (manufactured by Canon (Canon) Co., Ltd.), the obtained radiation-sensitive composition layer was exposed through a mask with a 1.1 μm square Bayer pattern ( The amount of exposure is the optimal amount of exposure that selects the line width to be 1.1μm).

Then, using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), the exposed radiation-sensitive composition layer was subjected to liquid-over development at 23° C. for 60 seconds. After that, rinsing was performed by rotating spray, and washed with pure water, and heated at 220° C. for 5 minutes on a hot plate to obtain a pattern.

(Example 102)

Using the spin coating method, the radiation sensitive composition of Example 1 was coated on a silicon wafer with an undercoating layer so that the film thickness after coating became 0.7 μm, and then it was applied on a hot plate at 100°C for 2 Minute heating to obtain a radiation-sensitive composition layer.

Then, I used the i-ray stepper exposure device FPA-3000i5+ (Canon) (Stock) Manufacturing), the obtained radiation-sensitive composition layer is exposed through a mask having a Bayer pattern of 1.1 μm square (the exposure amount is the optimal exposure amount that selects the line width to be 1.1 μm).

Then, using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), the exposed radiation-sensitive composition layer was developed for 60 seconds at 23°C. After that, the rinsing is carried out by rotating spray, and the washing is carried out with pure water. Furthermore, an i-ray stepping exposure device FPA-3000i5+ (manufactured by Canon Co., Ltd.) was used to ^{perform full-surface exposure at 1000 mJ/cm 2} , and then heated on a hot plate at 220° C. for 5 minutes to obtain a pattern.

In Example 101 and Example 102, patterns with excellent infrared shielding properties and rectangularity can be formed. In addition, in Example 101 and Example 102, a scanning electron microscope (SEM) was used to observe the cross section (pixel side wall) of the pattern part (magnification 25000). The result was that the rectangularity of Example 102 was compared with Example 101. good.

110: solid-state image sensor

111: Near infrared cut filter

112: Color filter

114: Infrared transmission filter

115: Micro lens

116: Planarization layer

hν: incident light

Claims (25)

A radiation-sensitive composition comprising a near-infrared absorber, a resin, a radical polymerizable compound, and a photo-radical polymerization initiator, and the radiation-sensitive composition has a maximum absorption wavelength in the range of 700 nm to 1000 nm, The ratio of the absorbance Amax at the maximum absorption wavelength to the absorbance A550 at a wavelength of 550 nm, that is, the absorbance Amax/absorbance A550 is 50 to 500, the resin includes a resin having an acid group, and the radical polymerizable compound has an acid The mass ratio of the resin of the radical is a radical polymerizable compound/resin having an acid radical=0.5 to 0.7. The radiation-sensitive composition according to claim 1, wherein the resin includes an alkali-soluble resin, and the mass ratio of the radical polymerizable compound to the alkali-soluble resin is radical polymerizable compound/alkali Soluble resin=0.3~0.7. A radiation-sensitive composition comprising a near-infrared absorber, a resin, a radical polymerizable compound, and a photo-radical polymerization initiator, and the radiation-sensitive composition has a maximum absorption wavelength in the range of 700 nm to 1000 nm, The ratio of the absorbance Amax at the maximum absorption wavelength to the absorbance A550 at a wavelength of 550 nm, that is, the absorbance Amax/absorbance A550 is 50 to 500, the resin includes a resin having an acid group, and the radical polymerizable compound has an acid The mass ratio of the resin of the base is radical polymerizable compound/resin with acid group=0.3~0.7, the resin includes alkali-soluble resin, and the alkali-soluble resin does not contain polymerization Sex-based. The radiation-sensitive composition described in item 3 of the scope of patent application, wherein the mass ratio of the radical polymerizable compound to the alkali-soluble resin is radical polymerizable compound/alkali-soluble resin=0.3 to 0.7. The radiation-sensitive composition according to any one of items 1 to 4 in the scope of patent application, wherein the photoradical polymerization initiator includes an oxime compound. The radiation-sensitive composition according to any one of items 1 to 4 in the scope of the patent application, wherein the photoradical polymerization initiator includes an oxime compound and an α-aminoketone compound. The radiation-sensitive composition according to any one of items 1 to 4 in the scope of the patent application, wherein the radical polymerizable compound is a radical polymerizable compound containing an acid group. The radiation-sensitive composition according to any one of items 1 to 4 of the scope of patent application, which further includes a chain transfer agent. The radiation-sensitive composition according to any one of items 1 to 4 of the scope of patent application, which further includes an ultraviolet absorber. The radiation-sensitive composition according to any one of items 1 to 4 in the scope of patent application, wherein the near-infrared absorber contains at least one selected from organic pigments and inorganic pigments. The radiation-sensitive composition according to any one of items 1 to 4 in the scope of the patent application, wherein the near-infrared absorber is contained at 20% by mass or more in the total solid content of the radiation-sensitive composition . The radiation-sensitive composition according to any one of items 1 to 4 of the scope of patent application, wherein the acid value of the alkali-soluble resin is 30 mgKOH/g to 500 mgKOH/g. The radiation-sensitive composition according to any one of items 1 to 4 in the scope of patent application, wherein the content of the radically polymerizable compound in the total solid content of the radiation-sensitive composition is 10 Mass%~35 mass%. The radiation-sensitive composition according to any one of items 1 to 4 of the scope of patent application, wherein the near-infrared absorber is a pyrrolopyrrole compound. The radiation-sensitive composition according to any one of items 1 to 4 in the scope of the patent application, wherein the near-infrared absorber is a compound represented by the following formula (5),

Rings A and B each independently represent an aromatic ring or a heteroaromatic ring, X ^A and X ^B each independently represent a substituent group, G ^A and G ^B independently represents a substituent group, kA represents 0 to an integer of nA, kB represents An integer from 0 to nB, nA and nB respectively represent the largest integers that can be substituted in ring A or ring B. X ^A and G ^A , X ^B and G ^B can be bonded to each other to form a ring, which exists ^{in G A} and G ^{B respectively} In the case of a plurality of them, they may be bonded to each other to form a ring structure. The radiation-sensitive composition according to claim 15, wherein in the formula (5), the ring A and the ring B are naphthalene rings, and the X ^A and X ^B each independently represent -NR ^X1 R ^X2, R ^X1 and R ^X2 said each independently represent a hydrogen atom or a substituent, and said kA represents the 1 kB, and the X ^A G ^A bonded to each other to form a ring, said X ^B and G ^{B is} bonded to each other to form a ring. An optical filter using the radiation-sensitive composition as described in any one of items 1 to 16 in the scope of the patent application. The optical filter according to the 17th patent application, wherein the optical filter is a near-infrared cut filter or an infrared transmission filter. The optical filter described in item 17 or item 18 of the scope of patent application further has an anti-reflection film. A laminate having a near-infrared cut filter using the radiation-sensitive composition described in any one of the scope of the patent application item 1 to item 16 and a color filter containing a color colorant. A pattern forming method, comprising: forming a radiation-sensitive composition layer on a support using the radiation-sensitive composition as described in any one of items 1 to 16 in the scope of the patent application; The step of exposing the radiation-sensitive composition layer; and the step of developing and removing the unexposed part to form a pattern. The pattern forming method as described in item 21 of the scope of patent application further includes a step of exposing after developing and removing the unexposed part. A solid-state imaging element, which has the 17th item in the scope of patent application The optical filter. An image display device having an optical filter as described in item 17 of the scope of patent application. An infrared sensor having an optical filter as described in item 17 of the scope of patent application.

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